CN105418035A - Method for manufacturing cement bricks from green mud and boiler ash recycled by utilization of pulping alkali - Google Patents

Method for manufacturing cement bricks from green mud and boiler ash recycled by utilization of pulping alkali Download PDF

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Publication number
CN105418035A
CN105418035A CN201511009550.0A CN201511009550A CN105418035A CN 105418035 A CN105418035 A CN 105418035A CN 201511009550 A CN201511009550 A CN 201511009550A CN 105418035 A CN105418035 A CN 105418035A
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green mud
cement
boiler ash
mud
content
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CN105418035B (en
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黄再桂
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GUANGXI JINGUI PULP PAPER CO Ltd
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GUANGXI JINGUI PULP PAPER CO Ltd
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    • 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
    • C04B28/04—Portland cements
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses a method for manufacturing cement bricks from green mud and boiler ash recycled by utilization of pulping alkali. The method is as follows: firstly, the following raw materials are weighed, by weight, 25-30% of green mud, 18-38% of boiler ash, 35-55% of limestone powder and 1-1.5% of cement, the above raw materials are mixed uniformly, and a mixture is obtained; secondly, the mixture is subjected to molding at a pressure of 40-50 MPa, and green bricks are obtained; thirdly, the green bricks are subjected to curing and cement bricks are obtained. The employed green mud does not need dewatering or alkalinity reduction, energy consumption is saved greatly, the brick manufacturing cost is lowered, the green mud doping amount is high, the cement doping amount is lowered than a conventional level, the waste utilization rate is raised greatly, the cement expense is saved, and the brick manufacturing cost is lowered further.

Description

Slurrying alkali collection green mud and boiler ash is utilized to make the method for cement brick
Technical field
The present invention relates to a kind of making method of cement brick, be specifically related to a kind of method utilizing slurrying alkali collection green mud and boiler ash to make cement brick.
Background technology
In pulping and paper-making production process, various solid waste can be produced, as mishandling, great pollution will be caused to environment.Solid waste mainly comprises the green mud in alkali collection workshop and the lime-ash of power boiler generation.Green mud is the waste produced after caustic room alkali collection in paper technology, is about about 5% containing alkali content, is mainly Ca (OH) 2and NaOH, water ratio is up to 70 ~ 80%, even higher, green mud complicated component, and the main chemical compositions in green mud butt and weight content are respectively: CaO40 ~ 45%, MgO3.8 ~ 4.2%, NaO5 ~ 6%, SiO 24 ~ 6%, Al 2o 31.0 ~ 2.0%, K 2o0.3 ~ 0.6%, Fe 2o 30.5 ~ 1.0%, loss on ignition is 35 ~ 45%.Green mud quality is fine and smooth, and viscosity is large, and granularity is little, and dehydration property is poor, is not easy to filter dehydration operation.Alkali collection causticization output green mud quantity is about 10kg/t slurry, and as arbitrarily toppled over, the other side or landfill can cause great harm to environment.Boiler ash comprises flyash and slag, mainly discharge from pulp and paper making power boiler, its quantity and composition depend on fuel used and combustion technology, the most pit ash content of China is higher, the cinder content that general coal combustion stays accounts for 20 ~ 35% of coal consumption, wherein 80 ~ 90% is flyash, and 10 ~ 20% is slag.
Green mud and boiler ash all can be used as cement brick, concrete material, the patent of invention being CN102627435A as publication number discloses a kind of pulping waste residues autoclaved brick and preparation method thereof, this autoclaved brick be less than with water ratio 2% green mud, the white clay that water ratio is less than 2%, flyash, basalt powder, blast-furnace slag and ordinary Portland cement are raw material, the weight percent of each raw material is: green mud 10 ~ 20%, white clay 5 ~ 10%, flyash 15 ~ 25%, basalt powder 35 ~ 55%, blast-furnace slag 8 ~ 12%, ordinary Portland cement 5%, the autoclaved brick ultimate compression strength made is 18.8MPa.The water ratio of the green mud that this autoclaved brick adopts is less than 2%, is almost dry mud, and dehydration difficulty is high, and energy consumption is large, and in addition, this autoclaved brick cement consumption is comparatively large, considerably increases brick making cost.And for example publication number is that the patent of invention of CN102503198A discloses compound green mud coal ash for concrete, this compound green mud coal ash be particle diameter is less than the Black Warrior rubble of 50mm and water ratio 15 ~ 25% wet-discharged coal ash, bottom slag and green mud co-grinding to powder fineness be that 45 microns of square hole sieves tail over and are less than 15%, carry out drying and processing in grinding process and use abrasive dust material water ratio and be less than 0.5%.In butt, each components based on weight percentage is respectively: basalt 30 ~ 75%, wet-discharged coal ash 10 ~ 50%, bottom slag 10 ~ 30%, green mud 1 ~ 10%.What this compound green mud coal ash for concrete adopted is the dry mud of green mud, and drying green mud needs to consume a large amount of energy, and meanwhile, the consumption of green mud is lower, cannot realize the at utmost utilization of refuse.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method utilizing slurrying alkali collection green mud and boiler ash to make cement brick, and the method does not need to carry out processed to green mud and can directly utilize, and the volume of green mud is comparatively large, significantly can save brick making cost.
Technical scheme provided by the invention is a kind of method that slurrying alkali collection green mud and boiler ash make cement brick,
1) weigh the raw material of following weight percent: by green mud 25 ~ 30%, boiler ash 18 ~ 38%, stone flour 35 ~ 55% and cement 1 ~ 2%, above-mentioned raw materials is mixed, obtains batch mixing;
2) by batch mixing at 40 ~ 50MPa forming under the pressure, obtain adobe;
3) maintenance is carried out in adobe, obtain cement brick.
After green mud mixes with particles such as boiler ash, stone flour, cement; containing a large amount of water in green mud; these water are wrapped in the hydration shell that small-particle surface forms thin layer; two have the public moisture film that there is superposition between the small-particle of hydration shell; due to small-particle top layer aquation membrane interaction; Al-O key and Si-O key are ruptured, generates AlO 2 -and SiO 3 2-ion, and then define the internal layer of small-particle electrostatic double layer and the counter-ion layet of electrostatic double layer, make small-particle have charging property, absorptivity and huge surface energy.Each mineralogical composition 3CaOSiO in cement 2, 2CaOSiO 2, 3CaOAl 2o 3, 4CaOAl 2o 3fe 2o 3rapidly with small-particle top layer moisture film generation hydration, generation gelinite and Ca (OH) 2, Ca (OH) 2the Ca of dissociation 2+carry out alkali exchange with the ion of small-particle top layer counter-ion layet immediately again, change short grained electrokinetic potential, form aggregate little one by one, impel SiO contained in aggregate 2, Al 2o 3, Fe 2o 3lateral reactivity Deng oxide compound is played, and continues and hydrolysis product of cement Ca (OH) 2water generation reaction Calucium Silicate powder, drated calcium aluminate and hydrated calcium ferrite, produce consolidation strength.Owing to containing a certain amount of Ca (OH) in green mud 2the Ca of dissociation 2+alkali exchange can be carried out with the ion of small-particle top layer counter-ion layet, form aggregate, and impel the SiO in aggregate 2, Al 2o 3, Fe 2o 3lateral reactivity Deng oxide compound is played, and continues and the Ca (OH) in green mud 2water generation reaction aggregate, not only greatly can strengthen the intensity of goods brick, also significantly reduce the consumption of cement.Along with synchronously carrying out of hydrated cementitious and alkali exchange interaction, hydrate just generates and gradually that water consumption is complete between moisture film, and the gelinite of generation and complete or incomplete crystal, impelled the development of cement umburned brick intensity.
In green mud, CaO content is high, SiO in flyash 2, Al 2o 3content is higher, CaO and SiO 2, Al 2o 3both are composite, thus make batch mixing reach suitable alkali coefficient and reactivity coefficient, thus greatly strengthen the intensity of finished bricks.
The water ratio of above-mentioned green mud is 70 ~ 80%, NaOH and Ca (OH) in green mud 2weight content be 4 ~ 5%.
Further, NaOH and Ca (OH) in green mud 2weight ratio 1:2 ~ 3, this proportioning can make there are enough Ca (OH) in batch mixing 2with enough Ca 2+, ensure comprehensively carrying out of hydration and alkali exchange interaction, improve the intensity of finished bricks.
In above-mentioned boiler ash, the content of flyash is 80 ~ 90%, and cinders content is 10 ~ 20%.
Further, in boiler ash, the content of flyash is 85 ~ 90%, and cinders content is 10 ~ 15%.
Above-mentioned cement is silicate cement.
Compared with prior art, the present invention has following beneficial effect:
1) green mud of the present invention's employing is without the need to dehydration, without the need to falling alkali, greatly having saved energy consumption, having reduced brick making cost.
2) green mud incorporation of the present invention is higher, and cement mixing content is well below conventional levels, substantially increases salvage value, has saved cement spending, reduce further brick making cost.
3) because water ratio in green mud is higher, therefore do not need additionally to add water, reduce water consumption.
4) the cement brick ultimate compression strength made of the present invention is large, good endurance.
Embodiment
The present invention is further elaborated for following specific embodiment, but not as a limitation of the invention.
Embodiment 1
1) weigh the raw material of following weight percent: by green mud 25%, boiler ash 19%, stone flour 55% and ordinary Portland cement 1%, above-mentioned raw materials is mixed, obtains batch mixing;
The water ratio of described green mud is 70%, NaOH and Ca (OH) in green mud 2weight content be 4%; In described boiler ash, the content of flyash is 80%, and cinders content is 20%; NaOH and Ca (OH) 2weight ratio 2:1.
2) by batch mixing at 40MPa forming under the pressure, obtain adobe.
3) adobe is carried out maintenance 28 days, obtain cement brick.
Embodiment 2
1) weigh the raw material of following weight percent: by green mud 28%, boiler ash 18%, stone flour 52.8% and ordinary Portland cement 1.2%, above-mentioned raw materials is mixed, obtains batch mixing;
The water ratio of described green mud is 80%, NaOH and Ca (OH) in green mud 2weight content be 5%; In described boiler ash, the content of flyash is 90%, and cinders content is 10%; NaOH and Ca (OH) 2weight ratio 1:1.
2) by batch mixing at 50MPa forming under the pressure, obtain adobe.
3) adobe is carried out maintenance 28 days, obtain cement brick.
Embodiment 3
1) weigh the raw material of following weight percent: by green mud 26%, boiler ash 38%, stone flour 35% and ordinary Portland cement 1%, above-mentioned raw materials is mixed, obtains batch mixing;
The water ratio of described green mud is 75%, NaOH and Ca (OH) in green mud 2weight content be 4.5%; NaOH and Ca (OH) 2weight ratio 1:2.
In described boiler ash, the content of flyash is 80%, and cinders content is 20%.
2) by batch mixing at 45MPa forming under the pressure, obtain adobe.
3) adobe is carried out maintenance 28 days, obtain cement brick.
Embodiment 4
1) weigh the raw material of following weight percent: by green mud 26%, boiler ash 38%, stone flour 35% and ordinary Portland cement 1%, above-mentioned raw materials is mixed, obtains batch mixing;
The water ratio of described green mud is 75%, NaOH and Ca (OH) in green mud 2weight content be 4.5%; NaOH and Ca (OH) 2weight ratio 1:3.
In described boiler ash, the content of flyash is 90%, and cinders content is 10%.
2) by batch mixing at 45MPa forming under the pressure, obtain adobe.
3) adobe is carried out maintenance 28 days, obtain cement brick.
Embodiment 5
1) weigh the raw material of following weight percent: by green mud 30%, boiler ash 33.5%, stone flour 35% and ordinary Portland cement 1.5%, above-mentioned raw materials is mixed, obtains batch mixing;
The water ratio of described green mud is 75%, NaOH and Ca (OH) in green mud 2weight content be 4.5%; NaOH and Ca (OH) 2weight ratio 1:2.5.
In described boiler ash, the content of flyash is 85%, and cinders content is 15%.
2) by batch mixing at 40MPa forming under the pressure, obtain adobe.
3) adobe is carried out maintenance 28 days, obtain cement brick.
Experimental example
1, the mensuration of water-intake rate
Make cement brick from embodiment 1 ~ 5 respectively and respectively select 5 pieces (standard size 240 × 115 × 53mm), often will organize 5 pieces of brick body test specimens as one group, brick body test specimen is dried first in an oven to constant weight, oven temperature is at 105 ~ 110 DEG C, time is 2h, and after cooling, namely the quality of test specimen is the dry mass m of test specimen., put into water tank by the test specimen end face after Drying and cooling down, water surface elevation is 1/3 of height of specimen, often through 12h, add highly for height of specimen 1/3 water until exceed summit.Immersion 24h after take out test specimen, wipe surface of test piece free water away, now the quality of test specimen be water suction saturated after mass M.The water-intake rate of brick represents with the mean value of 5 sample test results.
ε＝(M-m)/m×100％
Group ε(％)
Embodiment 1 13.12
Embodiment 2 13.20
Embodiment 3 11.08
Embodiment 4 11.13
Embodiment 5 11.11
2, the mensuration of ultimate compression strength fcu
From the cement brick that embodiment 1 ~ 5 is made, respectively select 1 piece (standard size 240 × 115 × 53mm) is respectively soaked in water, require that the immersion water surface should exceed test specimen top and be about 2.5mm, bleeding, it is saturated to carry out, and is removed by test specimen after 24h from water, wipes the free water of brick surface away.With reference to " measurement of the modulus of rupture and strength at break " in GB/T3810.4-1999, WE-10A type universal hydraulic testing machine is adopted to detect brick body ultimate compression strength.
Ultimate compression strength calculates: fcu=P/A
In formula: fcu-unconfined compression strength, MPa;
P---failing load, N;
A---test specimen load area, mm 2.
Group fcu(MPa)
Embodiment 1 16.80
Embodiment 2 17.20
Embodiment 3 19.68
Embodiment 4 19.92
Embodiment 5 19.89
3, brick Leaching Heavy Metals research
Carry out according to " solid waste Leaching leaching method: horizontal vibration method " (HJ557-2010): respectively select from the cement brick that embodiment 1 ~ 5 is made 1 piece (standard size 240 × 115 × 53mm) respectively, it is broken, cross 0.5mm sieve, take centre sample 15g respectively, be placed in tool lid wide mouth polyethylene bottles, adding distil water 150ml, makes solid-to-liquid ratio be 1:10 respectively.Bottles vertical is fixed on reciprocating vibrator, regulate oscillation frequency value 110 ± 10 times/min, amplitude 40mm, at room temperature vibrate 8h, leave standstill 16h, filter with middling speed quantitative paper, collect whole leach liquor, adopt microwave high pressure clear up-atomic absorption spectrophotometry measures leach liquor Cu, Zn, Cr, Cd, Pb, Ni respectively.Detected result is as follows:

Claims (6)

1. utilize slurrying alkali collection green mud and boiler ash to make the method for cement brick, it is characterized in that: comprise the following steps:
1) weigh the raw material of following weight percent: by green mud 25 ~ 30%, boiler ash 18 ~ 38%, stone flour 35 ~ 55% and cement 1 ~ 1.5%, above-mentioned raw materials is mixed, obtains batch mixing;
2) by batch mixing at 40 ~ 50MPa forming under the pressure, obtain adobe;
3) maintenance is carried out in adobe, obtain cement brick.
2. the method utilizing slurrying alkali collection green mud and boiler ash to make cement brick according to claim 1, is characterized in that: the water ratio of described green mud is 70 ~ 80%, NaOH and Ca (OH) in green mud 2weight content be 4 ~ 5%.
3. the method utilizing slurrying alkali collection green mud and boiler ash to make cement brick according to claim 2, is characterized in that: NaOH and Ca (OH) 2weight ratio 1:2 ~ 3.
4. the method utilizing slurrying alkali collection green mud and boiler ash to make cement brick according to claim 1, it is characterized in that: in boiler ash, the content of flyash is 80 ~ 90%, cinders content is 10 ~ 20%.
5. the method utilizing slurrying alkali collection green mud and boiler ash to make cement brick according to claim 4, it is characterized in that: in boiler ash, the content of flyash is 85 ~ 90%, cinders content is 10 ~ 15%.
6. the method utilizing slurrying alkali collection green mud and boiler ash to make cement brick according to claim 1, is characterized in that: described cement is silicate cement.
CN201511009550.0A 2015-12-29 2015-12-29 The method for making cement brick using slurrying alkali collection green mud and boiler ash Active CN105418035B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106673525A (en) * 2016-12-30 2017-05-17 海南金海浆纸业有限公司 Method for preparing lime sand brick by utilizing green slurrying mud and prepared lime sand brick
CN107266108A (en) * 2017-06-29 2017-10-20 合肥达户电线电缆科技有限公司 A kind of air-entrained concrete building block and preparation method thereof
CN111439969A (en) * 2020-04-07 2020-07-24 亚太森博（山东）浆纸有限公司 Resource treatment method for green mud of pulp mill
CN111439968A (en) * 2020-04-07 2020-07-24 亚太森博（山东）浆纸有限公司 Resourceful treatment method for slurry plant air-floated sludge

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101439947A (en) * 2007-11-22 2009-05-27 黄志鹏 Aerated concrete building block and manufacturing method thereof
CN102503198A (en) * 2011-11-08 2012-06-20 海南蓝岛环保产业股份有限公司 Compound green mud coal ash for concrete
CN102627435A (en) * 2012-04-20 2012-08-08 海南蓝岛环保产业股份有限公司 Paper pulp waste residue steam-pressing brick and preparation method thereof
CN103011706A (en) * 2012-12-14 2013-04-03 海南蓝岛环保产业股份有限公司 Concrete taking green mud and white mud as admixtures and preparation method for concrete

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101439947A (en) * 2007-11-22 2009-05-27 黄志鹏 Aerated concrete building block and manufacturing method thereof
CN102503198A (en) * 2011-11-08 2012-06-20 海南蓝岛环保产业股份有限公司 Compound green mud coal ash for concrete
CN102627435A (en) * 2012-04-20 2012-08-08 海南蓝岛环保产业股份有限公司 Paper pulp waste residue steam-pressing brick and preparation method thereof
CN103011706A (en) * 2012-12-14 2013-04-03 海南蓝岛环保产业股份有限公司 Concrete taking green mud and white mud as admixtures and preparation method for concrete

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106673525A (en) * 2016-12-30 2017-05-17 海南金海浆纸业有限公司 Method for preparing lime sand brick by utilizing green slurrying mud and prepared lime sand brick
CN107266108A (en) * 2017-06-29 2017-10-20 合肥达户电线电缆科技有限公司 A kind of air-entrained concrete building block and preparation method thereof
CN111439969A (en) * 2020-04-07 2020-07-24 亚太森博（山东）浆纸有限公司 Resource treatment method for green mud of pulp mill
CN111439968A (en) * 2020-04-07 2020-07-24 亚太森博（山东）浆纸有限公司 Resourceful treatment method for slurry plant air-floated sludge
CN111439968B (en) * 2020-04-07 2022-02-01 亚太森博（山东）浆纸有限公司 Resourceful treatment method for slurry plant air-floated sludge

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