CN102336532B - High-activity micro powder or cement produced by using papermaking waste residue and preparation method thereof - Google Patents
High-activity micro powder or cement produced by using papermaking waste residue and preparation method thereof Download PDFInfo
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- CN102336532B CN102336532B CN2011101819257A CN201110181925A CN102336532B CN 102336532 B CN102336532 B CN 102336532B CN 2011101819257 A CN2011101819257 A CN 2011101819257A CN 201110181925 A CN201110181925 A CN 201110181925A CN 102336532 B CN102336532 B CN 102336532B
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention discloses high-activity micro powder or cement produced by using papermaking waste residue and a preparation method thereof. The high-activity micro powder comprises the following raw materials in percentage by mass: 3 to 30 percent of causticized lime mud, 1 to 10 percent of sewage treatment waste residue, 10 to 60 percent of wet discharged fly ash, 10 to 60 percent of blast furnace slag, 2 to 5 percent of gypsum, 0.14 percent of grinding aid, and 1 percent of water reducing agent. The high-activity micro powder is prepared by drying of the raw materials, preheating decomposition reaction, proportioning of the raw materials and preparation of a finished product. The obtained high-activity micro powder or the cement has high strength and good activity; the cement also has good flowability and blending property and has no segregation or penetration; and the substitution quantity of the cement can reach 20 to 40 percent and even can reach over 50 percent, and the cement can be used for producing concrete of various types. Various indexes of the obtained high-activity micro powder or the cement accord with national related standards.
Description
Technical field
The present invention relates to a kind of New Building Materials and method thereof of utilizing industrial residue preparation, especially a kind of high-activity micro powder of producing with waste sludge from paper mill or cement and preparation method thereof.
Technical background
China is pulping and paper-making big country, according to statistics in 2008, annual 1000 ten thousand tons of the white claies that produce of whole nation papermaking, these white claies only have small part to obtain utilizing at present, major part all is outdoor stacking, not only take not a large amount of soils, contaminate environment, consuming a large amount of human and material resources, financial resources is managed, and wasted useful resources a large amount of in the white clay, if can rationally utilize this class white clay, not only solved white clay outlet and problem of environmental pollution, and can the decrease enterprise cost, improve enterprise competitiveness.
Paper white sludge derives from the recovery stage between the alkali recovery vehicle, black liquor of pulp making is through extracting evaporation concentration, obtain melts in the alkali recovery furnace roasting, then the water-soluble green liquor that is adds slaked lime and carries out the white depositions that causticizing reaction obtains in the green liquor and be the causticization white clay.Causticization white clay main component is as follows:
| Composition | CaO | MgO | Fe 2O 3 | Al 2O 3 | SiO 2 | Acid non-soluble substance | Loss on ignition |
| Ratio | 44.2~52.1 | 0.56~1.81 | 0.15~4.2 | 0.44~1.4 | 3.4~16.8 | 5.7~8.4 | 31.49~44.62 |
The sewage disposal waste residue that papermaking produces comprises: a large amount of throw outs when coagulation in the precipitation pool, and its main component is white clay and macrofiber; The second-stage treatment waste residue that has added the chemical reagent such as flocculation agent, Tai-Ace S 150, urea, tertiary sodium phosphate, its composition are complicated.
Flyash is the thin ash (generally referring to the thin ash that collect the coal-burning power plant from flue gas) in the flue gas that produces of coal combustion, and the chemical ingredients of general flyash mainly is: SiO
2, Al
2O
3, Fe
2O
3, CaO, MgO, SO
2Flyash mainly produces two kinds of mineral C through low-temperature heat treatment
2S and C
12A
7, CaSO especially
4When existing, the oxide compound in the flyash and gypsum aquation generate ettringite, are converted into C through subzero treatment
12Al
7, can magnanimous raising flyash activity and physical strength after levigate through maintenance certain length of time.
Blast-furnace slag is the industrial residue that discharges in the blast furnace ironmaking production process, is that cold through shrend is meal take Calucium Silicate powder as main melts, and its chemical ingredients mainly is: SiO
2, CaO, Al
2O
3, Fe
2O
3Deng, only have potential hydration activity, and active size is relevant with the vitreum content that Chemical Composition and shrend produce, must be under the basic material activation activity larger.
Summary of the invention
Paper white sludge is applied to has many people all in research in the production of cement, as utilizes white clay to replace Wingdale, calcining cement clinker, and production capacity is little but this method has high input, and the grog label is low, and cement cost is higher, can't promote; Blended material is made in utilizing in white clay and the flyash application manufacture of cement of also having, and because of the real principle of incorrect grasp, does not consider the hydration heat that cement produces in aquation, in addition the CaHCO in the white clay
3, Ca (OH)
2In cement concrete, shrink too fastly, produce easily crack performance, so that can't in actual production, use.
For paper white sludge and sewage disposal waste residue complicated, water content is higher, alkalescence is large, particle is little, can not get for a long time the deficiency effectively processed, the invention provides a kind of technique high-activity micro powder of producing with waste sludge from paper mill simple, with low cost or cement and preparation method thereof.
Realize that technical solution of the present invention is:
With the high-activity micro powder that waste sludge from paper mill is produced, the each component raw material by the quality proportioning is:
Causticization white clay 3%-30%; Sewage disposal waste residue 1%-10%; Wet-discharged coal ash 10%-60%; Blast-furnace slag 10%-60%; Gypsum 2%-5%; Grinding aid 0.14%; Water reducer 1%.
With the cement that waste sludge from paper mill is produced, the each component raw material by the quality proportioning is:
Causticization white clay 3%-30%; Sewage disposal waste residue 1%-10%; Wet-discharged coal ash 10%-50%; Blast-furnace slag 10%-50%; Cement clinker 10%-30%; Gypsum 2%-5%; Grinding aid 0.14%; Water reducer 1%.
The method that preparation is produced high-activity micro powder with waste sludge from paper mill, its processing step is as follows:
The first step: raw material stoving and pre-pyrolysis:
1) the causticization white clay that papermaking is produced 200 ℃-800 ℃ dry to moisture content less than 2%-7%;
2) the sewage disposal waste residue that papermaking is produced 200 ℃-800 ℃ dry to moisture content less than 2%-7%;
3) with power plant's wet-discharged coal ash 140 ℃-400 ℃ dry to moisture content less than 2%-5%, enter and carry out anoxic activation in the storage tank more than 6 hours;
4) with blast-furnace slag 120 ℃-200 ℃ dry to moisture content less than 1%-3%;
Second step: feed proportioning
To dry with pre-pyrolysis after the gained raw material, by causticization white clay 3%-30%; Sewage disposal waste residue 1%-10%; Wet-discharged coal ash 10%-60%; Blast-furnace slag 10%-60%; The proportion ingredient of gypsum 2%-5% is made compound;
The 3rd step: finished product is manufactured
Proportioning adding grinding aid, water reducer and compound by grinding aid 0.14%, water reducer 1% carry out grinding, namely make the high-activity micro powder finished product.
The method that preparation is produced cement with waste sludge from paper mill,
The first step: raw material stoving and pre-pyrolysis:
1) the causticization white clay that papermaking is produced 200 ℃-800 ℃ dry to moisture content less than 2%-7%;
2) the sewage disposal waste residue that papermaking is produced 200 ℃-800 ℃ dry to moisture content less than 2%-7%;
3) with power plant's wet-discharged coal ash 140 ℃-400 ℃ dry to moisture content less than 2%-5%, enter and carry out anoxic activation in the storage tank more than 6 hours;
4) with blast-furnace slag 120 ℃-200 ℃ dry to moisture content less than 1%-3%;
Second step: feed proportioning
With the raw material of gained behind oven dry and the pre-pyrolysis, by causticization white clay 3%-30%; Sewage disposal waste residue 1%-10%; Wet-discharged coal ash 10%-50%; Blast-furnace slag 10%-50%; Cement clinker 10%-30%; The proportion ingredient of gypsum 2%-5% is made compound;
The 3rd step: finished product is manufactured
The proportioning of pressing grinding aid 0.14%, water reducer 1% adds grinding aid, water reducer, carries out grinding with compound and namely makes finished cement.
Adopt the beneficial effect of method of the present invention to be: the present invention compared with prior art, its remarkable advantage has: micro mist and cement products cost that (1) adopts present method to make are low, the micro mist cost of producing than existing ordinary skill hangs down about about 60 yuan/T; (2) present method processing paper white sludge and Sewage waste residue products obtained therefrom market adaptability are extensive, and cost performance is superior, and generalization is good; (3) present method can thoroughly solve alkali and reclaim the problem of environmental pollution that the causticization white clay causes, and has realized again effective utilization of causticization white clay; (4) present method processing paper white sludge and sewage disposal waste residue amount are very large, can carry out according to the enterprise of local centralized production papermaking waste residue processes, present method is applicable take timber and non-timber as causticization white clay and sewage disposal waste residue that raw material oar processed produces, is applicable to the alkali recovery causticization white clay of large and medium-sized papermaking enterprise and the processing of sewage disposal waste residue.It is good that the high-activity micro powder that the present invention obtains or cement have an intensity height, active good, concrete flowability, workability, without the segregation excreting water phenomenon, cement replacement amount can reach 20%-40%, have in addition can reach more than 50%, can produce the concrete of all kinds of models.The high-activity micro powder that the present invention obtains or cement indices meet relative national standards.
Embodiment
The below describes in further detail the present invention.
Method and technology thinking of the present invention: dry causticization white clay, sewage disposal waste residue, wet-discharged coal ash, blast-furnace slag, activate in advance (1).(2) utilize the causticization white clay to contain part calcium hydroxide and residual alkali, the raw materials such as active silica, aluminum oxide activate wet fly-ash, blast-furnace slag activity.(3) the Sewage waste residue can slow down micro mist in concrete shrinking percentage and time of coagulation.(4) utilize the sodium lignosulfonate in the Sewage waste residue and add water reducer, grinding aid and improve the active of micro mist and reduce water requirement, improve concrete slump rate.(5) utilize the siliceous height of causticization white clay and part to activate Ca (OH)
2With pozzolanic activity materials such as wet fly-ash and blast-furnace slags, in the concrete hydrating process, can produce the hydrated calcium silicate gel material.(6) adopt new and effective micronizer to improve the micro mist specific surface area, greatly improve the micro mist activity.
Papermaking causticization white clay as referred to herein refers to obtain the causticization white clay by concentrated press filtration or vacuum press filtration, contains part unreacted completely calcium hydroxide and residual alkali, water ratio 35%-55%; The Sewage waste residue refers to that papermaking enterprise is in disposing of sewage, mud major ingredient in the coagulation precipitation pool is white clay and macrofiber, add the waste residue that the part industrial chemicals produces in the second-stage treatment, major ingredient is relevant with the raw material of adding, and composition is complicated; Wet-discharged coal ash refers to the rudimentary wet fly-ash that precipitates by the water comb; Blast-furnace slag refers to the industrial residue that discharges in the steel-making enterprise blast furnace ironmaking production process, is that cold through shrend is meal take Calucium Silicate powder as main melts, and its Chemical Composition mainly is SiO
2, CaO, Al
2O
3, Fe
2O
3
The principle of the invention utilizes the sewage disposal waste residue to produce, itself be exactly to add the product that a certain amount of flocculation agent, urea, Tai-Ace S 150, Ling acid trisodium are disposed of sewage, and how much have the molecule of a certain amount of calcium lignin sulphonate in the sewage, and these compositions can both effectively be controlled water requirement, time of coagulation, hydration heat of product etc.
The micro mist indices that the present invention produces meets GB S75 level, S95 level, S105 level.
The every physical index of cement that the present invention produces meets national standard " general cement standard ".
With high-activity micro powder and the method thereof of causticization white clay and the preparation of sewage disposal waste residue, its step is as follows:
Papermaking causticization white clay is carried out hyperthermia drying at fluidizing furnace, make that the calcium carbonate decomposed is calcium hydroxide in the causticization white clay.Temperature Control of Drying Oven is at 200 ℃-800 ℃, dry to moisture content less than 3%, place dry vessel.
The Sewage waste residue is carried out hyperthermia drying at fluidizing furnace, and the macrofiber in the activation waste residue makes it to produce a certain amount of wooden calcium, workization Ling acid three sodium molecules.Temperature is controlled at 200 ℃-800 ℃, dry to moisture content less than 5%, place dry vessel.
Wet-discharged coal ash is carried out glass crystal in the pre-activated wet fly ash of middle temperature oven dry at fluidizing furnace, Temperature Control of Drying Oven is at 140 ℃-400 ℃, drop temperature is controlled at about 75 ℃, dry to moisture content less than 2%, enter and carry out anoxic activation in the hold-up vessel more than 6 hours.
Blast-furnace slag is carried out oven drying at low temperature at fluidizing furnace, because excess Temperature is dried the too drastic activity that can destroy glass crystal in the slag and will be carried out iron removal step simultaneously.Temperature Control of Drying Oven in the time of 120 ℃-200 ℃, dry to moisture content less than 1%, place dry vessel.
The according to the form below ratio is made compound with causticization white clay, sewage disposal waste residue, wet-discharged coal ash, blast-furnace slag, gypsum batching, add again 0.14% grinding aid, 1% water reducer, carried out grinding 40 minutes with compound, to specific surface area be more than the 540 ㎡/㎏, 0.003mm tails over and can not surpass 10%.
| Title | Proportioning 1 | Proportioning 2 | Proportioning 3 | Proportioning 4 |
| The causticization white clay | 3% | 30% | 12% | 16% |
| The sewage disposal waste residue | 1% | 10% | 3% | 8% |
| Wet-discharged coal ash | 33% | 43.86% | 59.86% | 10% |
| Blast-furnace slag | 59.86% | 10% | 20% | 59.86% |
| Gypsum | 2% | 5% | 4% | 5% |
| Grinding aid | 0.14% | 0.14% | 0.14% | 0.14% |
| Water reducer | 1% | 1% | 1% | 1% |
Performance index are as follows:
With cement and the method thereof of causticization white clay and the preparation of sewage disposal waste residue, its step is as follows:
Papermaking causticization white clay is carried out hyperthermia drying at fluidizing furnace, make that the calcium carbonate decomposed is calcium hydroxide in the causticization white clay.Temperature Control of Drying Oven is at 200 ℃-800 ℃, dry to moisture content less than 3%, place dry vessel.
The Sewage waste residue is carried out hyperthermia drying at fluidizing furnace, and the macrofiber in the activation waste residue makes it to produce a certain amount of wooden calcium, workization Ling acid three sodium molecules.Temperature is controlled at 200 ℃-800 ℃, dry to moisture content less than 5%, place dry vessel.
Wet-discharged coal ash is carried out glass crystal in the pre-activated wet fly ash of middle temperature oven dry at fluidizing furnace, Temperature Control of Drying Oven is at 140 ℃-400 ℃, drop temperature is controlled at about 75 ℃, dry to moisture content less than 2%, enter and carry out anoxic activation in the hold-up vessel more than 6 hours.
Blast-furnace slag is carried out oven drying at low temperature at fluidizing furnace, because excess Temperature is dried the too drastic activity that can destroy glass crystal in the slag and will be carried out iron removal step simultaneously.Temperature Control of Drying Oven in the time of 120 ℃-200 ℃, dry to moisture content less than 1%, place dry vessel.
The according to the form below ratio is made compound with causticization white clay, sewage disposal waste residue, wet-discharged coal ash, blast-furnace slag, cement clinker, gypsum batching, add again 0.14% grinding aid, 1% water reducer, carried out grinding 40 minutes with compound, to specific surface area be more than the 430 ㎡/㎏.
| Title | Proportioning 1 | Proportioning 2 | Proportioning 3 | Proportioning 4 |
| The causticization white clay | 3% | 13% | 30% | 16% |
| The sewage disposal waste residue | 2% | 8% | 10% | 8% |
| Wet-discharged coal ash | 10% | 49.86% | 25.86% | 29.86% |
| Blast-furnace slag | 49.86% | 10% | 20% | 20% |
| Grog | 30% | 15% | 10% | 20% |
| Gypsum | 4% | 3% | 3% | 5% |
| Grinding aid | 0.14% | 0.14% | 0.14% | 0.14% |
| Water reducer | 1% | 1% | 1% | 1% |
Performance index are as follows:
The example water requirement detects is undertaken by GB GB/T 1346.
The example specific surface area detects is undertaken by GB GB/T 8074.
Example detection time of coagulation is undertaken by GB GB/T 1346.
The example degree of mobilization detects and is undertaken by GB GB/T 2419.
The example intensity detection is undertaken by GB GB/T 17671.
The prescriptive procedure that the example activity index detects by authorized by state carries out.
Claims (2)
1. high-activity micro powder of producing with waste sludge from paper mill, it is characterized in that: the each component raw material by the quality proportioning is: causticization white clay 3%-30%; Sewage disposal waste residue 1%-10%; Wet-discharged coal ash 10%-60%; Blast-furnace slag 10%-60%; Gypsum 2%-5%; Grinding aid 0.14%; Water reducer 1%.
2. cement of producing with waste sludge from paper mill, it is characterized in that: the each component raw material by the quality proportioning is: causticization white clay 3%-30%; Sewage disposal waste residue 1%-10%; Wet-discharged coal ash 10%-50%; Blast-furnace slag 10%-50%; Cement clinker 10%-30%; Gypsum 2%-5%; Grinding aid 0.14%; Water reducer 1%.
3
.A kind of production method for preparing the described high-activity micro powder of claim 1 is characterized in that:
The first step: raw material stoving and pre-pyrolysis:
1) the causticization white clay that papermaking is produced 200 ℃-800 ℃ dry to moisture content less than 3%;
2) the sewage disposal waste residue that papermaking is produced 200 ℃-800 ℃ dry to moisture content less than 5%;
3) with power plant's wet-discharged coal ash 140 ℃-400 ℃ dry to moisture content less than 2%, enter and carry out anoxic activation in the storage tank more than 6 hours;
4) with blast-furnace slag 120 ℃-200 ℃ dry to moisture content less than 1%;
Second step: feed proportioning
To dry with pre-pyrolysis after gained causticization white clay, sewage disposal waste residue, wet-discharged coal ash, blast-furnace slag and gypsum are made compound by the described proportion ingredient of claim 1;
The 3rd step: finished product is manufactured
Add grinding aid, water reducer and compound by the described proportioning of claim 1 and carry out grinding, namely make the high-activity micro powder finished product.
4
.A kind of production method for preparing the described cement of claim 2,
The first step: raw material stoving and pre-pyrolysis:
1) the causticization white clay that papermaking is produced 200 ℃-800 ℃ dry to moisture content less than 3%;
2) the sewage disposal waste residue that papermaking is produced 200 ℃-800 ℃ dry to moisture content less than 5%;
3) with power plant's wet-discharged coal ash 140 ℃-400 ℃ dry to moisture content less than 2%, enter and carry out anoxic activation in the storage tank more than 6 hours;
4) with blast-furnace slag 120 ℃-200 ℃ dry to moisture content less than 1%;
Second step: feed proportioning
To dry with pre-pyrolysis after gained causticization white clay, sewage disposal waste residue, wet-discharged coal ash, blast-furnace slag and gypsum and cement clinker, make compound by the described proportion ingredient of claim 2;
The 3rd step: finished product is manufactured
Add grinding aid, water reducer by the described proportioning of claim 2, carry out grinding with compound and namely make finished cement.
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|---|---|---|---|
| CN2011101819257A CN102336532B (en) | 2011-06-30 | 2011-06-30 | High-activity micro powder or cement produced by using papermaking waste residue and preparation method thereof |
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| CN102336532B true CN102336532B (en) | 2013-04-10 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586947A (en) * | 2012-03-09 | 2012-07-18 | 鹤壁维洁节能材料研究院 | Method for producing inorganic fiber for papermaking by means of alkali recovery lime sludge of paper mill |
| CN103011706B (en) * | 2012-12-14 | 2014-08-13 | 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 |
| CN103406332B (en) * | 2013-08-09 | 2015-04-01 | 金东纸业（江苏）股份有限公司 | Method for recycling waste residues generated in papermaking and object obtained with the method |
| CN103880356B (en) * | 2014-02-25 | 2015-11-18 | 冯乃谦 | A kind of method utilizing paper white sludge to manufacture multifunctional concrete |
| CN103979810A (en) * | 2014-05-22 | 2014-08-13 | 同济大学 | Method for preparing sulphoaluminate cement clinker by comprehensively utilizing papermaking white mud, bauxite and flue gas desulfurization gypsum |
| CN105645798B (en) * | 2016-03-10 | 2017-09-01 | 吴兵 | A kind of method that utilization pulping and paper-making white clay produces flyash |
| CN110482886B (en) * | 2019-08-21 | 2021-10-01 | 湖州乌米科技有限公司 | Method for preparing high-strength cement by using papermaking waste |
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| KR20040110643A (en) * | 2003-06-20 | 2004-12-31 | 장미희 | Method and composite for manufacture of cement |
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