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

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.