CN106946479A - A kind of humble thermal expansion portland cement - Google Patents

A kind of humble thermal expansion portland cement Download PDF

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Publication number
CN106946479A
CN106946479A CN201710219340.7A CN201710219340A CN106946479A CN 106946479 A CN106946479 A CN 106946479A CN 201710219340 A CN201710219340 A CN 201710219340A CN 106946479 A CN106946479 A CN 106946479A
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China
Prior art keywords
humble
thermal expansion
parts
portland cement
solid sulfur
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CN201710219340.7A
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Chinese (zh)
Inventor
蒋旺林
段守富
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Mianyang Moshi Technology Co Ltd
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Mianyang Moshi Technology Co Ltd
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Priority to CN201710219340.7A priority Critical patent/CN106946479A/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
    • C04B7/02Portland cement
    • C04B7/04Portland cement using raw materials containing gypsum, i.e. processes of the Mueller-Kuehne type
    • 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
    • C04B7/36Manufacture of hydraulic cements in general
    • C04B7/38Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a kind of humble thermal expansion portland cement, by weight, including following components:40 ~ 70 parts of Portland clinker, 20 ~ 30 parts of solid sulfur ash, 10 ~ 30 parts of flyash, 0 ~ 3 part of gypsum, 0.1 ~ 1 part of exciting agent, 5 ~ 15 parts of metakaolin.The present invention turns waste into wealth using trade waste solid sulfur ash as primary raw material, reduces cost so that high financial profit, compared with like product, with more the market competitiveness, meanwhile, environmental pollution is reduced, is that the utilization of solid sulfur ash opens up a new way;The preparation of low heat micro expanding cement only needs to grinding, is not required to calcining, and simple production process, energy consumption is relatively low, can save the substantial amounts of energy;Preparation technology is simple, and easily operation, practical;Using developing a circular economy, effectively using industrial residue, a new utilization ways are provided for solid sulfur ash, are the popularization widening road of circulating fluidized bed combustion coal technology.

Description

A kind of humble thermal expansion portland cement
Technical field
The present invention relates to engineering material technical field, a kind of humble thermal expansion portland cement is specifically referred to.
Background technology
Early in 1936, French Losail made raw material in revolution with 50% gypsum, 25% red bauxite and 25% chalk first Mature calcined material in kiln, then with the slag and portland cement clinker intergrinding of proper proportion, is manufactured that expanding cement. The Ke Laien and its colleague of California, USA university in 1958 have invented K-type expanding cement on the basis of Luo Saile, its Manufacturing process and chemical composition are similar to the cement of Losail.It is Japanese then after it have purchased the patent of gram Lay by research and change Enter, have developed calcium sulphoaluminate cement, and unlike technique produced in USA, Japan, will after calcining sulfoaluminate clinker It is individually milled into sulphur aluminium calcium expansive agent for cement slurry, and as commodity cement mixing into expanding cement.It now yet there are no use Industrial residue is humble thermal expansion cement of good performance prepared by raw material.
The content of the invention
It is an object of the invention to provide one kind by raw material of industrial residue, simple production process, low cost, product quality It is functional, and the humble thermal expansion portland cement of energy-conserving and environment-protective.
The present invention is achieved through the following technical solutions:A kind of humble thermal expansion portland cement, by weight, including with Lower component:
40 ~ 70 parts of Portland clinker
20 ~ 30 parts of solid sulfur ash
10 ~ 30 parts of flyash
0 ~ 3 part of gypsum
0.1 ~ 1 part of exciting agent
5 ~ 15 parts of metakaolin.
Humble thermal expansion portland cement of the present invention is prepared, then need to only be mixed it by above-mentioned parts by weight dispensing Uniformly, produce.
The theoretical foundation of the present invention and the mechanism of chemical reaction are as follows:
Contain bloodstone, f-CaO, II-CaSO4 and active al2o3 etc., the master of its expansion produced after adding water in solid sulfur ash Reacting has:
CaSO4+H2O→CaSO4·H2O;2.26 times of volumetric expansion
CaO+H2O→Ca(OH)2;1.98 times of volumetric expansion
mCa(OH)2+Al2O3+nH2O→mCaO·Al2O3·nH2O;
3CaO·Al2O3·6H2O+3CaSO4·2H2O→3CaO·Al2O3·3CaSO4·32H2O;
2.22 times of volumetric expansion.
As can be seen that solid sulfur ash has larger dilatancy in itself, more active Al is contained from the point of view of its composition2O3、SO3 Content is also higher.Secondly, the SO contained in solid sulfur ash3With anhydrite II-CaSO4Form is present, and has identical with natural anhydrite Structure, can replace dihydrate gypsum that cement setting time is adjusted completely, and can be with active Al2O3、SO3Reaction generation Entringite.
Current research and experiment are proved:Entringite has the expansile feature of stability, in drying, humidity, high temperature, low Under the various mal-conditions such as temperature, the crystal structure of entringite is difficult to destroy, and with other hydrolysis mineral C-S-H in cement Coordinating can make cement produce higher intensity and expansion character.Therefore, it can to control content of the entringite in cement minerals and Make cement that there is expansion character and produce seif-citing rate, increase the compactness of cement, so as to increase the intensity of cement, impervious and sulfur resistive The ability of hydrochlorate etch.Cause the destruction to cement in order to avoid the expansion energy of entringite is excessive, except control entringite Growing amount outside, while the expansion reaction that C3A must be made to change into entringite controls plastic stage in cement and elastic limit Completed within intensity.
Pass through the constituent analysis to CFBC solid sulfur ash, it is believed that can be by aluminum, sulphur matter raw material to solid sulphur Aluminium and sulphur in ash carry out certain correction and are prepared into the expanding cement that entringite is main expansion sources, and this patent selects higher ridge Soil is used as aluminum raw material.
Metakaolin is the product that kaolin is dehydrated formation at high temperature, and with pozzolanic activity, it is mixed can after cement So that significantly time of hydrated cementitious induction period to be shortened, but also can shift to an earlier date hydration heat peak and entringite be split into peak, Under such environment, the hydration heat speed of slurry gradually relaxes.
Circulating fluidized bed combustion ash refers to sulfur-bearing coal and sulphur-fixing agent(Usually lime stone)After mixing according to a certain percentage, The solid waste discharged in fluidized-bed combustion boiler after 850-900 DEG C of combustion desulfurization, is included in the solid sulphur that flue is collected into Ash and the CFB residues discharged from furnace bottom.Because ignition temperature is not up to the temperature of coal formation liquid phase in CFBB, The fluidized bed combustion coal ash/slag discharged is relative to the discarded object produced in 1300 DEG C or so burnings of coal dust --- for flyash, its each side Performance has bigger difference.Fluidized bed combustion coal ash/slag is generally in loose porous shape, therefore water requirement is far above flyash;Nothing in solid sulfur ash is determined Shape SiO2 and A12O3 make it have pozzolanic activity, and hydration reaction generation C- can occur in the presence of calcium carbonate exciting agent S-H and C-A-H gels;The main presence in the form of II-CaSO4 of sulphur in solid sulfur ash.II-CaSO4 indissolubles and aquation are slow, its Hydrated product entringite and dihydrate gypsum are the main expansion sources of solid sulfur ash;Calcium content in solid sulfur ash is far above flyash, is The important sources of the white hardness of solid sulfur ash.
In order to which the present invention is better achieved, further, the specific surface area of the Portland clinker for 300kg/m2 ~ 350kg/m2, the specific surface area of solid sulfur ash is 380kg/m2 ~ 430kg/m2.
In order to which the present invention is better achieved, further, the intensity of the Portland clinker meets 42.5 intensity etc. The requirement of class g cement.
In order to which the present invention is better achieved, further, wherein SO3 content < 3.5%.
In order to which the present invention is better achieved, further, CaO content < 10% in the flyash, SO3 contents < 3%, f- CaO content < 1%.
In order to which the present invention is better achieved, further, the specific surface area of the gypsum is 200 ~ 400m2/Kg。
In order to which the present invention is better achieved, further, the gypsum is anhydrite, dihydrate gypsum, ardealite and desulfurization At least one in gypsum.
In order to which the present invention is better achieved, further, the exciting agent is in potassium sulfate, NaOH and waterglass It is at least one.
The present invention compared with prior art, with advantages below and beneficial effect:
(1)The present invention turns waste into wealth using trade waste solid sulfur ash as primary raw material, reduces cost so that high financial profit, with Like product compares, with more the market competitiveness, meanwhile, environmental pollution is reduced, is that the utilization of solid sulfur ash opens one newly Approach;
(2)Using the present invention, the preparation of low heat micro expanding cement only needs to grinding, be not required to calcining, simple production process, energy consumption compared with It is low, the substantial amounts of energy can be saved;
(3)Product preparation process of the present invention is simple, and easily operation, practical;Using developing a circular economy, industry is effectively utilized Waste residue, a new utilization ways are provided for solid sulfur ash, are the popularization widening road of circulating fluidized bed combustion coal technology.
Embodiment
The present invention is described in further detail with reference to embodiment, but embodiments of the present invention not limited to this, Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, various replace is made Change and change, all should be included within the scope of the invention.To make the purpose of the present invention, process conditions and advantage effect clearer Understand, with reference to following embodiment, the present invention is described in further detail.Specific implementation example described herein is only used to The present invention is explained, is not intended to limit the present invention.
Embodiment 1:
The present embodiment prepares humble thermal expansion portland cement, by weight, including following components:
Flyash:10 parts;Solid sulfur ash:20 parts;70 parts of clinker;1 part of gypsum;Exciting agent:0.2 part;Metakaolin:7 parts.
Said components are well mixed, humble thermal expansion portland cement needed for producing.The presetting period of the cement is 1 small When 30 minutes, final setting time is 55 minutes 2 hours, and 3 days and the rupture strength of 28 days are respectively 4.2MPa and 8.6MPa, 3 days and The compression strength of 28 days is respectively 25MPa and 48MPa, 1 day, 7 days with the linear expansivity of 28 days be respectively 0.13%, 0.17% with 0.44%。
Embodiment 2:
The present embodiment prepares humble thermal expansion portland cement, by weight, including following components:
Flyash:10 parts;Solid sulfur ash:25 parts;65 parts of clinker;0.5 part of gypsum;Exciting agent:0.3 part;Metakaolin:10 parts.
Said components are well mixed, humble thermal expansion portland cement needed for producing.The presetting period of the cement is 2 small When 5 minutes, final setting time is 40 minutes 3 hours, and 3 days and the rupture strength of 28 days are respectively 4.1MPa and 9.9MPa, 3 days and 28 It compression strength is respectively 27MPa and 53MPa, 1 day, 7 days with the linear expansivity of 28 days be respectively 0.16%, 0.22% with 0.52%。
Embodiment 3:
The present embodiment prepares humble thermal expansion portland cement, by weight, including following components:
Said components are well mixed, humble thermal expansion portland cement needed for producing.The presetting period of the cement is 2 hours 55 Minute, final setting time is 10 minutes 6 hours, and 3 days are respectively 4.0MPa and 8.9MPa, 3 days and 28 days with the rupture strength of 28 days Compression strength be respectively 24MPa and 53MPa, 1 day, 7 days with the linear expansivity of 28 days is respectively 0.18%, 0.25% and 0.58%.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that:Not A variety of change, modification, replacement and modification can be carried out to these embodiments by departing under the principle and objective of the present invention, of the invention Scope is limited by claim and its equivalent.
The invention discloses a kind of humble thermal expansion portland cement, by weight, including following components:Silicate cement 40 ~ 70 parts of mud clinker, 20 ~ 30 parts of solid sulfur ash, 10 ~ 30 parts of flyash, 0 ~ 3 part of gypsum, 0.1 ~ 1 part of exciting agent, metakaolin 5 ~ 15 parts.The present invention turns waste into wealth using trade waste solid sulfur ash as primary raw material, reduces cost so that high financial profit, and same Class product compares, with more the market competitiveness, meanwhile, environmental pollution is reduced, is that the utilization of solid sulfur ash opens one newly Approach;The preparation of low heat micro expanding cement only needs to grinding, is not required to calcining, and simple production process, energy consumption is relatively low, can save big The energy of amount;Preparation technology is simple, and easily operation, practical;Using developing a circular economy, effectively using industrial residue, it is Solid sulfur ash provides a new utilization ways, is the popularization widening road of circulating fluidized bed combustion coal technology.

Claims (8)

1. a kind of humble thermal expansion portland cement, it is characterised in that by weight, including following components:
40 ~ 70 parts of Portland clinker
20 ~ 30 parts of solid sulfur ash
10 ~ 30 parts of flyash
0 ~ 3 part of gypsum
0.1 ~ 1 part of exciting agent
5 ~ 15 parts of metakaolin.
2. a kind of humble thermal expansion portland cement according to claim 1, it is characterised in that the portland cement is ripe The specific surface area of material is 300kg/m2~350kg/m2, the specific surface area of solid sulfur ash is 380kg/m2~430kg/m2
3. a kind of humble thermal expansion portland cement according to claim 1 or 2, it is characterised in that the silicate cement The intensity of mud clinker meets the requirement of 42.5 strength rating cements.
4. a kind of humble thermal expansion portland cement according to claim 1 or 2, it is characterised in that wherein SO3Content < 3.5%.
5. a kind of humble thermal expansion portland cement according to claim 1 or 2, it is characterised in that in the flyash CaO content < 10%, SO3 content < 3%, f-CaO contents < 1%.
6. a kind of humble thermal expansion portland cement according to claim 1 or 2, it is characterised in that the ratio of the gypsum Surface area is 200 ~ 400m2/Kg。
7. a kind of humble thermal expansion portland cement according to claim 1 or 2, it is characterised in that the gypsum is hard At least one in gypsum, dihydrate gypsum, ardealite and desulfurated plaster.
8. a kind of humble thermal expansion portland cement according to claim 1 or 2, it is characterised in that the exciting agent is At least one in potassium sulfate, NaOH and waterglass.
CN201710219340.7A 2017-04-06 2017-04-06 A kind of humble thermal expansion portland cement Pending CN106946479A (en)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN109399976A (en) * 2018-12-18 2019-03-01 武汉理工大学 A kind of roadbase fluidized bed combustion coal ash/slag slow setting micro-expansion cement and preparation method thereof
CN109912243A (en) * 2019-03-19 2019-06-21 西卓子山草原水泥集团包头三固有限责任公司 A kind of cement produced using Industrial Solid Waste
CN111116117A (en) * 2019-12-18 2020-05-08 山东大学 Chemically-excited sulfur-fixing ash-slag-based foamed light soil
CN113788634A (en) * 2021-09-01 2021-12-14 长江三峡技术经济发展有限公司 Micro-expansion cement prepared by utilizing sulfur-fixing ash and preparation method of cement
CN115784645A (en) * 2022-12-15 2023-03-14 山西路桥再生资源开发有限公司 Method for improving utilization rate of waste residues to research and develop ecological cement
CN116986850A (en) * 2023-06-08 2023-11-03 碳达(深圳)新材料技术有限责任公司 Composite concrete and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109399976A (en) * 2018-12-18 2019-03-01 武汉理工大学 A kind of roadbase fluidized bed combustion coal ash/slag slow setting micro-expansion cement and preparation method thereof
CN109912243A (en) * 2019-03-19 2019-06-21 西卓子山草原水泥集团包头三固有限责任公司 A kind of cement produced using Industrial Solid Waste
CN111116117A (en) * 2019-12-18 2020-05-08 山东大学 Chemically-excited sulfur-fixing ash-slag-based foamed light soil
CN111116117B (en) * 2019-12-18 2021-02-26 山东大学 Chemically-excited sulfur-fixing ash-slag-based foamed light soil
CN113788634A (en) * 2021-09-01 2021-12-14 长江三峡技术经济发展有限公司 Micro-expansion cement prepared by utilizing sulfur-fixing ash and preparation method of cement
CN115784645A (en) * 2022-12-15 2023-03-14 山西路桥再生资源开发有限公司 Method for improving utilization rate of waste residues to research and develop ecological cement
CN116986850A (en) * 2023-06-08 2023-11-03 碳达(深圳)新材料技术有限责任公司 Composite concrete and preparation method thereof

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Application publication date: 20170714