CN101328029B - Preparation of manganese slag groundmass geopolymer cementing material - Google Patents

Preparation of manganese slag groundmass geopolymer cementing material Download PDF

Info

Publication number
CN101328029B
CN101328029B CN2008100736927A CN200810073692A CN101328029B CN 101328029 B CN101328029 B CN 101328029B CN 2008100736927 A CN2008100736927 A CN 2008100736927A CN 200810073692 A CN200810073692 A CN 200810073692A CN 101328029 B CN101328029 B CN 101328029B
Authority
CN
China
Prior art keywords
manganese slag
water
water glass
kaolin
mixed
Prior art date
Application number
CN2008100736927A
Other languages
Chinese (zh)
Other versions
CN101328029A (en
Inventor
陈平
刘荣进
马帅
贾韶辉
安庆锋
李海东
王一靓
Original Assignee
桂林工学院
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 桂林工学院 filed Critical 桂林工学院
Priority to CN2008100736927A priority Critical patent/CN101328029B/en
Publication of CN101328029A publication Critical patent/CN101328029A/en
Application granted granted Critical
Publication of CN101328029B publication Critical patent/CN101328029B/en

Links

Classifications

    • 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
    • C04B12/00Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/005Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/24Sea water resistance
    • 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

Abstract

The invention discloses a method for preparing a manganese slag-based geological polymer binder comprising: (1) the solid components of the materials are manganese slag and kaolin; the liquid components are water glass, water and activator. (2) the manganese slag is dried till the moisture content is less than 1%, and is milled in a ball mill till the specific surface is 400-600m<2>/kg, the kaolin is calcined at 900 DEG C till the kaolin becomes metakaolin, and is milled till the specific surface is 500-700<2>/kg. (3) the activator is added into the water glass solution and is mixed uniformlywith water to get a water glass solution with a water glass modulus value of 1.5-3.5 and a water glass baume of 35-45 degrees. (4) the mixed solution prepared by the step (3) is added into the mixed powder of managese and metakaolin micropowder, is stirred and moulded after uniform mixture and maintenance. The preparation method has advantages of simple technology, no pollution during the preparation process, good gelling property and strong anti-seawater erosion property using industrial waste residue.

Description

The preparation method of manganese slag groundmass geopolymer cementing material
Technical field
The invention belongs to the inorganic non-metallic class, relate to a kind of preparation method of manganese slag groundmass geopolymer cementing material.
Background technology
During the modern architecture material industry was produced, cement was a very important class base mateiral.Resource, the energy that manufacture of cement consumption is a large amount of, cement manufacturing industry energy consumption total amount accounted for 75.5% of building materials industry energy consumption total amount in 2005.China's cement output accounts for first place, the world for many years, add up cement output the year ends 2006 and reached 12.4 hundred million tons, and The world other various countries cement output in 2006 has 13,28 hundred million tons, we can say, almost half of world's cement is in China.Yet Cement industry has become the important factor that influences climate change and bad environment pollution, a large amount of CO of cement production process discharging 2Become the arch-criminal of greenhouse gases, produced simultaneously SO 2, obnoxious flavoures such as NOx have also produced disadvantageous effect to Air quality, and China is the second largest country of consumption in the world today, and is very important to this problem.
Ferromanganese ore slag is the special slag of a class, and it is the granular particle that manganeseirom is formed through water quick cooling by the slag that is discharged in high-temperature smelting process, claims the manganese slag again because of manganese monoxide content is higher.Ferromanganese ore slag possesses latent hydraulicity and volcanic ash through behind the shrend chilling, is the higher material of a kind of activity, and is the same with slag, flyash equal industrial residue, has the value of application and development.Manganese slag quantity is about 2-2.5 times of manganeseirom output, national manganeseirom output was 8,650,000 tons in 2004, produce the manganese slag and be about 1,700 ten thousand tons, the manganese slag is used for cement mixture and melts down the smelting except that about 30%, other 70% are made heap and fill out processing, by this estimate whole nation then the clean quantity discharged of manganese slag be about 1,200 ten thousand tons.The manganese slag utilizes situation to cause anxiety, and economize as the abundantest emerging manganese sparetime university of national manganese resource in Guangxi, and the most of employing of institute's manganese slag that produces is piled and filled out processing in the ferroalloy smelting process.Along with expanding economy, series society, economy and environmental problem that the discharging of manganese slag causes begin to show especially out, and heap occupies with a large amount of soils on the one hand, increases enterprise cost, and open-air heap is filled out and then caused " slag mountain " in blocks to occur; On the other hand, piling Mn, the Cr element filled out in the manganese slag is easy to run off polluted water under the rainwater effect.
Geopolymer is to be main raw material with aluminium silicate mineral or industrial solid castoff, prepare burden with kaolinite, do the stay in place form agent with water glass, make activator with alkaloids such as sodium hydroxide, through batching, mixing, add water and stir moulding, an and class ceramic that forms by aquation polymerization, dehydration sclerosis within a certain period of time.Since the seventies in 20th century, domestic and international large quantities of scholars study geopolymer, bear fruit in the research of blast-furnace slag, slag, flyash equal industrial residue.This material forming process is: the dissolving complexing of aluminosilicate solid ingredient, disperse migration, concentrate polymerization and dehydration sclerosis, the matrix phase that forms mutually by dehydrated form, be three-dimensional net structure on the physical aspect, with undissolved solid particulate gluing is hard block, is the architecture basics that material obtains good mechanical performance and chemical stability.Geopolymer is a kind of extraordinary material, material character and one such as collection superpolymer, pottery, cement, and every performance index are outstanding.
Summary of the invention
Purpose of the present invention is exactly to have weather and the environmental problem that manganese slag utilization ratio is not high and manufacture of cement caused now in order to solve, and providing a kind of is the manganese slag groundmass geopolymer preparation methods of main raw material with manganese slag, kaolin.
Concrete steps of the present invention are:
(1) raw material is made up of solid ingredient and liquid ingredient two portions, and the solid ingredient mass percentage content is as follows: manganese slag 50~90%, kaolin 10~50%; Liquid ingredient is made up of exciting agent, water glass and water, and liquid ingredient is 25%~40% of a solid ingredient mass percent; Liquid ingredient content by volume is as follows: water glass 20~60%, water 40~80%, exciting agent are 0~4% of solid ingredient mass percent; Exciting agent is KOH, NaOH, Na 2SO 4, CaSO 4In a kind of;
(2) the manganese slag is dried to water ratio less than 1%, put into the ball mill grinding to specific surface area 400~600m 2/ Kg; Get kaolin and be fired to metakaolin, and grinding to specific surface area is 500~700m at 650~900 ℃ 2/ Kg;
(3) exciting agent is mixed in the water glass, and itself and water are mixed, obtain modulus of water glass and be 1.5~2.5, the water glass mixing solutions of 35~45 ° of degree Beaume;
(4) mixing solutions that step (3) is configured slowly joins in the mixed powder of manganese slag and metakaolin micro mist, stirs 60~90 seconds, and the back preparation moulding that mixes, stirs gets final product through maintenance.
The present invention adopts water glass, KOH, the agent of NaOH equal excitation that manganese slag, metakaolin are excited and can make, and strength grade reaches more than the 62.5MPa, and its stability is good, and time of coagulation and intensity are qualified.Each component of solid ingredient and liquid ingredient all seals storage and transport respectively, and preparation manganese slag groundmass geopolymer material carries out with field mix, whipped form.
Wherein, exciting agent act as: the alkaline environment of material reaction is provided, accelerates the depolymerization-polycondensation process of metakaolin in basic solution, OH is provided -Make polymer formation initial network structure; Acting as of metakaolin: the raw material that the polymer formation structure is provided; The manganese slag act as: discharge Ca 2+, promoting polymer formation, water forms the silicates mineral simultaneously, and OH is provided -
Manganese slag groundmass geopolymer be a kind of be main frame form's the netted structure glue gel material in space with Si-O tetrahedron and Al-O tetrahedron, the manganese slag starting stage is embedded in the structure as weighting material, grow with time and form the undefined structure hydrated product gradually, the special construction hardenite of this product is more closely knit.The forming process of whole system can be with the chemical formula brief summary:
The invention has the beneficial effects as follows:
(1) adopts nothing calcining, normal temperature prepared gelling material, realize " environmental protection, energy-conservation " target.
(2) can utilize this industrial residue of manganese slag to prepare manganese slag groundmass geopolymer in a large number, incorporation helps improving environment, save energy 50~90%.
(3) Pei Zhi manganese slag groundmass geopolymer cementing material strength grade meets GB 175-2007 52.5 ordinary Portland cement national standards fully, and anti-marine denudation is good.
Embodiment
Embodiment 1:
(1) solid ingredient is prepared burden by weight percentage, manganese slag 70%, kaolin 30%; Liquid ingredient is the per-cent batching by volume, water glass 40%, water 60%; Water cement ratio 0.45, exciting agent chemical pure KOH is 4% of a solid ingredient mass percent;
(2) the manganese slag is dried to water ratio less than 1%, put into the ball mill grinding to specific surface area 450m 2/ Kg; Get kaolin and form metakaolin, and grinding to specific surface area is 500m 650 ℃ of calcinings 2/ Kg;
(3) exciting agent chemical pure KOH is mixed in the water glass, and itself and water are mixed, obtain the water glass mixing solutions of 40 ° of moduluss of water glass 3.25, degree Beaume;
(4) mixing solutions that step (3) is configured slowly joins in the mixed powder of manganese slag and metakaolin micro mist, stirs 60 seconds, mixes aftershaping, and 20 ℃ of temperature, maintenance got final product in 28 days under the environment of humidity 90%.
The manganese slag groundmass geopolymer and the standard sand that prepare are carried out the proportioning molding with weight ratio at 1: 2.5.3 days ultimate compression strength 49.3MPa of institute's glue sand test block, anti-folding 3.5MPa; 7 days ultimate compression strength 62.3MPa, folding strength 4.9MPa; 28 days ultimate compression strength 63.6MPa, folding strength 6.0MPa.
Embodiment 2:
(1) solids component is prepared burden by weight percentage, and the manganese slag accounts for 90%, kaolin 10%; Press liquid ingredient per-cent batching by volume, water glass 40%, water 60%, water cement ratio 0.45, exciting agent accounts for 4% of solids component mass percent for chemical pure NaOH.
(2) the manganese slag is dried to water ratio less than 1%, put into the ball mill grinding to specific surface area 600m 2/ Kg; Get kaolin and form metakaolin 900 ℃ of calcinings, and grinding.To specific surface area be 700m 2/ Kg.
(3) exciting agent chemical pure NaOH is mixed in the water glass, and itself and water are mixed, obtain modulus of water glass and be 3.25, the water glass mixing solutions of 40 ° of degree Beaume.
(4) mixing solutions that step (3) is configured slowly joins in the mixed powder of manganese slag and metakaolin micro mist, stirs 90 seconds, mixes aftershaping, and 20 ℃ of temperature, maintenance got final product in 28 days under the environment of humidity 90%.
The manganese slag groundmass geopolymer and the standard sand that prepare are carried out the proportioning molding with weight ratio at 1: 2.5.3 days ultimate compression strength 49.6MPa of institute's glue sand test block, anti-folding 4.3MPa; 7 days ultimate compression strength 65.9MPa, folding strength 6.5MPa; 28 days ultimate compression strength 68.6MPa, folding strength 7.1MPa.
More than two routine manganese slag adulterant volumes 70~90%, prepared gelling material ultimate compression strength satisfies the PO52.5 cement standard fully, and stability is good.
Embodiment 3:
(1) solids component is prepared burden by weight percentage, and the manganese slag accounts for 80%, kaolin 20%; Percentage calculation by volume: water glass accounts for 40%, and water accounts for 60%, water cement ratio 0.45, and wherein exciting agent accounts for 4% of solids component mass percent for chemical pure KOH;
(2) with weight percent be 90% manganese slag dry to water ratio less than 1%, put into the ball mill grinding to specific surface area 600m 2/ Kg; Get weight percent and be 10% kaolin and be fired to metakaolin, and grinding to specific surface area is 700m at 900 ℃ 2/ Kg.
(3) exciting agent chemical pure NaOH is mixed in the water glass, and itself and water are mixed, obtaining modulus of water glass is 3.25, the water glass mixing solutions that degree Beaume is 40 °.
(4) mixing solutions that step (3) is configured slowly joins in the mixed powder of manganese slag and metakaolin micro mist, stirs 90 seconds, mixes aftershaping, and 20 ℃ of temperature, maintenance got final product in 28 days under the environment of humidity 90%.
The manganese slag groundmass geopolymer for preparing and standard sand are carried out the proportioning molding with weight ratio at 1: 2.5 put into seawater (form according to seawater artificial synthetic) immersion 30 days, 60 days, 90 days.30 days ultimate compression strength 74.6MPa of institute's glue sand test block, anti-folding 3.46MPa; 60 days ultimate compression strength 92.80MPa, folding strength 4.10MPa; 90 days ultimate compression strength 104.6MPa, folding strength 6.10MPa.This example explanation utilizes the strength development under the marine denudation situation of the manganese slag groundmass geopolymer influence that well do not weather.

Claims (1)

1. the preparation method of a manganese slag groundmass geopolymer cementing material is characterized in that concrete steps are:
(1) raw material is made up of solid ingredient and liquid ingredient two portions, and the solid ingredient mass percentage content is as follows: manganese slag 50~90%, kaolin 10~50%; Liquid ingredient is made up of exciting agent, water glass and water, and liquid ingredient is 25%~40% of a solid ingredient mass percent; Liquid ingredient content by volume is as follows: water glass 20~60%, water 40~80%, exciting agent are 0~4% of solid ingredient mass percent; Exciting agent is KOH, NaOH, Na 2SO 4, CaSO 4In a kind of;
(2) the manganese slag is dried to water ratio less than 1%, put into the ball mill grinding to specific surface area 400~600m 2/ Kg; Get kaolin and form metakaolin, and grinding to specific surface area is 500~700m 650~900 ℃ of calcinings 2/ Kg;
(3) exciting agent is mixed in the water glass, and itself and water are mixed, obtain modulus of water glass and be 1.5~2.5, the water glass mixing solutions of 35~45 ° of degree Beaume;
(4) mixing solutions that step (3) is configured slowly joins in the mixed powder of manganese slag and metakaolin micro mist, stirs 60~90 seconds, and the back preparation moulding that mixes, stirs gets final product through maintenance.
CN2008100736927A 2008-07-18 2008-07-18 Preparation of manganese slag groundmass geopolymer cementing material CN101328029B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008100736927A CN101328029B (en) 2008-07-18 2008-07-18 Preparation of manganese slag groundmass geopolymer cementing material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008100736927A CN101328029B (en) 2008-07-18 2008-07-18 Preparation of manganese slag groundmass geopolymer cementing material

Publications (2)

Publication Number Publication Date
CN101328029A CN101328029A (en) 2008-12-24
CN101328029B true CN101328029B (en) 2010-08-04

Family

ID=40204081

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008100736927A CN101328029B (en) 2008-07-18 2008-07-18 Preparation of manganese slag groundmass geopolymer cementing material

Country Status (1)

Country Link
CN (1) CN101328029B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073205A (en) * 2013-02-04 2013-05-01 连云港金红矿业有限公司 Preparation method of omphacite geopolymer material

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102627426B (en) * 2012-03-22 2013-10-09 内蒙古科技大学 Slag-coal ash compound solid exciter and preparation method thereof
CN102690100A (en) * 2012-06-22 2012-09-26 桂林理工大学 Method for preparing inorganic polymer material by taking bayer red mud and kaolin as main raw materials
CN103130479B (en) * 2013-01-31 2014-10-15 贵州大学 Formula and production technology for preparing mineral polymer materials with manganese residue
CN105272125A (en) * 2015-09-30 2016-01-27 中国地质大学(武汉) Geopolymer-based rapid repairing material and preparation method thereof
CN105271848A (en) * 2015-10-22 2016-01-27 桂林理工大学 Manganese gangue slag-based geopolymer cementing material and preparation method thereof
CN105621912B (en) * 2015-12-25 2017-12-29 南宁学院 A kind of preparation method for avoiding ground polymers starch foam particle composite thermal insulation material caused by lamination
CN105601187B (en) * 2015-12-25 2017-12-29 南宁学院 A kind of preparation method for the ground polymers starch foam particle composite thermal insulation material for adding density enhancing
CN105503126B (en) * 2015-12-25 2017-11-03 南宁学院 A kind of insulation, low cigarette, low toxicity ground polymers starch foam particulate composite and preparation method thereof
CN105565763A (en) * 2015-12-28 2016-05-11 南宁学院 High-compatibility geopolymer-starch foam particle composite heat-preserving material and preparation method thereof
CN105776909B (en) * 2016-01-31 2017-09-01 西安建筑科技大学 The preparation of electrical conductivity controllable alkali-activated carbonatite manganese slag base composite semiconductor binder materials
CN106277861A (en) * 2016-08-15 2017-01-04 马鞍山十七冶工程科技有限责任公司 A kind of Novel geological polymer and preparation method
CN106565192A (en) * 2016-11-06 2017-04-19 桂林理工大学 Kaolin/manganese tailing-straw external composite heat-insulation material for building external wall
CZ2016771A3 (en) * 2016-12-07 2018-02-07 Unipetrol výzkumně vzdělávací centrum, a.s. A two-component geopolymer binder for the production of plastic geopolymers
CN108947286A (en) * 2017-05-23 2018-12-07 北方民族大学 It is a kind of based on manganese slag, the geo-polymer gel rubber material of flyash and its preparation method and application
CN108951371A (en) * 2018-09-12 2018-12-07 杭州固益强新材料科技有限公司 A kind of extrusion method for geo-polymer site operation
CN109160774A (en) * 2018-09-12 2019-01-08 杭州固益强新材料科技有限公司 A kind of injection geo-polymer
CN110066146A (en) * 2019-04-23 2019-07-30 南昌大学 The recycling of tungsten slag and reuse method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103073205A (en) * 2013-02-04 2013-05-01 连云港金红矿业有限公司 Preparation method of omphacite geopolymer material
CN103073205B (en) * 2013-02-04 2014-07-16 连云港金红矿业有限公司 Preparation method of omphacite geopolymer material

Also Published As

Publication number Publication date
CN101328029A (en) 2008-12-24

Similar Documents

Publication Publication Date Title
Wang et al. The role of fly ash microsphere in the microstructure and macroscopic properties of high-strength concrete
Pangdaeng et al. Influence of curing conditions on properties of high calcium fly ash geopolymer containing Portland cement as additive
Ahmari et al. Production of eco-friendly bricks from copper mine tailings through geopolymerization
Al Bakri et al. The processing, characterization, and properties of fly ash based geopolymer concrete
Rao et al. Final setting time and compressive strength of fly ash and GGBS-based geopolymer paste and mortar
Sata et al. Properties of pervious geopolymer concrete using recycled aggregates
Phoo-ngernkham et al. Properties of high calcium fly ash geopolymer pastes with Portland cement as an additive
CN102701656B (en) Metakaolin-based polymer foam concrete and preparation method thereof
Patankar et al. Effect of concentration of sodium hydroxide and degree of heat curing on fly ash-based geopolymer mortar
CN101948331B (en) Autoclaved aerated concrete building block and preparation method thereof
Ma et al. Preparation of cleaner one-part geopolymer by investigating different types of commercial sodium metasilicate in China
Van Chanh et al. Recent research geopolymer concrete
Rajamma et al. Alkali activation of biomass fly ash–metakaolin blends
Bui et al. Manufacture and performance of cold bonded lightweight aggregate using alkaline activators for high performance concrete
CN103159443B (en) Ultrahigh-strength concrete and preparation method thereof
CN103771817B (en) A kind of desulfurated plaster foam concrete and preparation method thereof
CN103086655B (en) A kind of concrete brick and preparation method thereof
CN102276224B (en) Marine engineering self-compacting high-performance concrete and preparation method thereof
CN101781109B (en) Light-weight dry-mixed masonry mortar
Mustafa Al Bakri et al. Effect of Na 2 SiO 3/NaOH Ratios and NaOH Molarities on Compressive Strength of Fly-Ash-Based Geopolymer.
CN103011896B (en) Foam concrete
CN100445232C (en) Mine debris steamed brick and its production method
CN103601424A (en) Geopolymeric concrete based on recycled aggregate and preparation method of geopolymeric concrete
CN103803904A (en) Self-compacting light aggregate concrete and preparation method thereof
CN101863072B (en) Internal curing process for improving performance of high strength and slight expansion concrete

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100804

Termination date: 20180718