CN1260158C - New type of ecological cement and its prepn and application - Google Patents
New type of ecological cement and its prepn and application Download PDFInfo
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- CN1260158C CN1260158C CNB2004100360681A CN200410036068A CN1260158C CN 1260158 C CN1260158 C CN 1260158C CN B2004100360681 A CNB2004100360681 A CN B2004100360681A CN 200410036068 A CN200410036068 A CN 200410036068A CN 1260158 C CN1260158 C CN 1260158C
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Abstract
The present invention relates to novel ecological cement, a preparing method thereof and an application thereof. The novel ecological cement belongs to the technical field of gel materials. The novel ecological cement comprises materials F with rich aluminum, materials P with poor aluminum and guide crystal seed materials D, wherein the materials F and P are selected from various industrial solid waste materials and have inherent reification characteristics of various original natural minerals in the nature. Materials are combined and processed, the materials F have the proportioning molar ratio of Si to Ca of 0.5 to 1.7 and the proportioning molar ratio of Si to Al of 3.0 to 1.5, and the materials P have the proportioning molar ratio of Si to Ca of 1.0 to 0.3 and the proportioning molar ratio of Si to Al of 1.0 to 2.6. Gelatinous substances with high strength are formed by watering and fully mixing the materials F, P and D during use. In production, all materials are industrial waste materials and natural minerals basically, and secondary pollution on environment can not occur no longer. The present invention really realizes the comprehensive use of waste and realizes real clean and ecological production without environment pollution.
Description
(1) technical field
The present invention relates to a kind of eco-cement and preparation method thereof and application, belong to field of cementing material technology.
(2) background technology
All under physics, chemical action, can become firm Shi Zhuanti from slurry, and can glued unclassified stores and material with certain physical strength, be referred to as gelling material, gelling material is divided into two kinds of the hydraulicity and on-hydraulics, ordinary Portland cement, aluminate cement belong to hydraulic material, mix can not only in air, harden behind the water again can be in water the hardened material.
Since 19th-century end portland cement was born, up to the present cement, remained the most large in the world building structural materials as the history in existing more than 100 year of building cementing material.Through very long historical development and repeatedly major transformation, cement and cement concrete production technology reach its maturity and are perfect, but portland cement inherent defective also reveals day by day.Because traditional silicate cement sintering technology complexity, energy consumption is big, discharges a large amount of obnoxious flavour contaminate environment, destroys the eubiosis, has brought the harm that grows with each passing day to global biosphere.
Wuzhong big academician once pointed out before death: " over past ten years, China's Cement industry is gone on the unsustainable road for development of a high yield, high consumption, poor efficiency, high carrying capacity of environment, must be by the in addition transformation of essence of scientific and technical innovation." for many years, the building materials scientific worker adopt in cement the partially mixed material of admixture or in concrete admixture part active admixture, be used to improve the chemical constitution of cement matrix, reduce the sintered clinker consumption, all be effective measure.But these practice great majority are to be main purpose to reduce cost, and fundamentally do not change the composition of cement matrix, realize high-performance, so the compounding process that development cement and high-performance are used is the cement matrix composition of fundamentally thorough reform traditional and an important channel of high-performance use technology.
The development of cement and the development of human civilization are undivided, however its pollution that development brought and the destruction of ecotope become the formidable opponent that the restriction civilized society further develops again.Silicate cement came out over more than 100 year, and cement production process has experienced repeatedly and changed.Its know-why of technology of comparative maturity is based on the active constituent tricalcium silicate in the cement clinker and Dicalcium Phosphate (Feed Grade) mineral or tricalcium aluminate at present, under the effect of mineralizer, 1250-1400 ℃ of formation, in whole Cement Production process, through three processes of grinding of raw material preparation and grinding, clinker burning process and finished cement.In the process of burning till with grinding, just caused pollution to the realistic survival environment, resource utilization is low, and the energy consumption height is as a large amount of dust, SO
2, NO
X, CO
2Deng the killer that all will become ecotope.Current no matter be silicate cement, or aluminate cement, all to pass through said process, after particularly reforming and opening up to the outside world, along with the continuous replacement of equipment, the quick growth of the increasing of social demand amount, social economy's total amount, Portland cement and special cement output increase severely day by day, the live wire of small cement plant starts, and when satisfying economic construction, has also increased the weight of the difficulty of environmental pollution and improvement.
In recent years, the industrialization of cement produced with the dry method production technique has solved the expensive subproblem of technology in the past on cost, but still there is same environmental pollution in same burning mill joint process.Cement is as three big basic materials of building industry, and the every field that involves the interests of the state and the people civilian, military, water conservancy etc. plays crucial effect, and of many uses, consumption increases, and Cement industry also increases for social harm.The harm of China's Cement industry is mainly reflected in obnoxious flavour and the pollution of heavy metal, the waste of ample resources and non-renewable, the dust pollution that causes thus of generation.According to seeing among the GB175-1999, in existing cement production process flow process, the Dust Capacity that oven dry and calcining produce accounts for the 70%-80% of cement mill total release, and these add the state that mostly is in direct discharging from the dust of operations such as grinding, fragmentation, in this case, China's cement dust quantity discharged will reach 1,500 ten thousand tons/year, and most of cement mill all are the dischargings of high density, have had a strong impact on ecotope.
In addition, China's cement output has been broken through 600,000,000 tons at present, then year consume about 600,000,000 tons of Wingdale, the coal of 2.5 hundred million tons of clays and 100,000,000 tons, these resources all are human most important resources, the future that is related to human development, the use of resource has just caused serious scarcity of resources like this, causes the damage of material ecological chain easily, resource seriously unbalance brings uncertain disaster to the mankind.
The a large amount of SO that discharge in the cement industry
2, NO
X, CO
2, having very strong toxicity, the acid rain of formation and acid mist are to human body, large-area animals and plants, and various ecological vegetations can work the mischief, in China, because a large amount of SO
2The discharging of high density makes that the area has become acid rain district occurred frequently, CO greatly
2Discharging can produce Greenhouse effect, can allow the mankind can't bear NO in the course of time
X, gases such as HF become increasingly conspicuous to the influence of environmental quality.
In China, cement sectors adopt a large amount of refractory materials magnesia chrome bricks, magnesia chrome brick in use is easy to sulphur in conjunction with forming the sexavalent chrome salt compound, and is very easily water-soluble, flows into water resources, can cause a large amount of metal poisonings, cause the generation of various diseases, even cancer, there is not relevant criterion in China as yet to Pb, the Sn of cement industry, the discharging of V, Sb etc., do not have enough knowledge, this also is the big hidden danger that cement industry exists.
Equally in China, a large amount of trade wastes are deposited in the open, caused the red mud that produces in serious air, ground, the pollution of waterhead, particularly alumina producing, be a hang-up in the world always, the technology that always adopts the open pile dam to deposit for a long time, caused for surrounding enviroment to have a strong impact on, and constantly taken a large amount of arable lands, and caused the waste of underground water source, along with the increase of aluminum oxide output, will have a large amount of red muds in continuous discharging; The a large amount of slag that also has the discharging of ferrous metallurgy industry, as titanium ore slag, phosphorus ore slag, Water Quenching Slag etc., all environment is caused severe contamination, depositing in a large number at a large amount of flyash of coal electric industry in addition,, cause another invisible killer of environmental pollution beyond doubt, how the waste residue that also has various chemical industries all in a large amount of accumulations with depositing, utilizes these solid trade wastes to become each common problem of paying close attention to of row all circles as phosphorus slag, coal gangue, chemical waste gypsum or the like.
In addition, at nature, still there is a large amount of natural resourcess to utilize, but prior art still fails it is utilized, as in China, particularly in area, basin along rivers,lakes and seas, form all kinds of shale on the geology, low-quality kaolin, the volcanic ash raw material is not just well utilized at present, also has the waste of a large amount of Industrial buildings rubbish and silicate industry depositing in a large number equally, has had a strong impact on integrated environment, and caused the serious wasting of resources, human survival makes full use of existing mineral wealth and carries out nature remodeling in the world of a resource scarcity, beautifies the human lives and also becomes an important problem.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of eco-cement and preparation method thereof and application are provided.
Eco-cement of the present invention comprises rich aluminum feedstock F material, lean aluminum material P material and guiding crystal seed D material, wherein,
F material is a mixture of selecting for use one or more materials in red mud, slag, ironmaking Water Quenching Slag, flyash, titanium ore slag, phosphorus slag, shale, slag, clay, volcanic ash material, bauxite, building waste and the waste concrete that the alumina producer of unformed shape or micritization discharges to form, batching mol ratio [Si]/[Ca]=0.5-1.7, [Si]/[Al]=3.0-1.5.
The P material is a mixture of selecting one or more compositions in bauxite, slag, limestone mine, waste soda residue, phosphorus slag, chemical gypsum, cement clinker, carbonate, silicate, aluminate, phosphoric acid salt and the halogen class for use, batching mol ratio [Si]/[Ca]=1.0-0.3, [Si]/[Al]=4.0-2.6.
Above-mentioned phosphorus slag and/or slag are not placed in F material and the P material simultaneously.
Above-mentioned phosphorus slag is the waste residue in the production of phosphate fertilizer.Waste soda residue is the waste residue that soda ash is produced in solvay soda process.
The weight ratio of F material, P material, D material is as follows:
The F material: P material=10-99: 1-80, preferred F material: P material=60-89: 11-40,
D material: (F material+P material)=1-30: 70-99, preferred D material: (F material+P material)=1-10: 90-99.
The D material is by high reactivity Al (OH)
3, highly basic, water glass and Tai-Ace S 150 are synthesized into, and at first are by high reactivity Al (OH)
3, highly basic in reactive tank, carry out chemical combination in the 60-120 ℃ of scope, and then add solid or liquid soluble glass, add the crystallization degree that Tai-Ace S 150 is adjusted crystal seed at last, be incubated 10-60 hour, temperature is controlled at 40-80 ℃.Each composition weight percent is as follows:
High reactivity Al (OH)
3: 20-45%
Highly basic: 15-25%
Water glass: 20-40%
Tai-Ace S 150: 10-15%.
Modulus (the SiO of above-mentioned solid or liquid soluble glass
2/ NaO) M=1.0-2.5.
The weight percent of above-mentioned F material, P material water content is 0.1-70%, preferred 0.1-45%.
Above-mentioned F material and P material can have additive when grinding, mainly be to be used for metering needle to condensation condition and the color and the abrasive of customer requirements, and mainly be sodium aluminate, sodium methyl silicate, calcium saccharate, polyvinyl acetate, active A l (OH)
3, calcium chloride, oxalic dialdehyde, in ligninsulfonate, highly basic, quickened lime breast, sodium polyphosphate, borate and the trolamine one or more.
The additive add-on of above-mentioned F material and P material is decided as the case may be, can account for the weight percent 0.5-10% of F material or P material.
The chemical ingredients of above-mentioned raw materials essential substance sees the following form: (calculating by weight percentage)
| Title | SiO 2 | Fe 2O 3 | Al 2O 3 | GaO | MgO | TiO 2 | Na 2O | K 2O | Igloss |
| Red mud | 10-12 | 10-15 | 8-15 | 30-50 | 1-3 | 5-10 | 4-9 | 1-3 | 0-15 |
| Flyash | 20-60 | 1-15 | 10-40 | 1-15 | 0.5-3 | 1-2 | 1-5 | 0.5-2 | 0-10 |
| Shale | 25-65 | 2-8 | 8-20 | 2-30 | 0.5-2 | 0.3-1 | 1-5 | 1-5 | 0-25 |
| Slag | 20-60 | 1-15 | 10-40 | 1-15 | 0.5-3 | 1-2 | 1-5 | 0.5-2 | 0-10 |
| Water Quenching Slag | 20-45 | 0.1-3 | 5-25 | 35-50 | 2-15 | 1-5 | 1-5 | 0.4-2 | 0-8 |
| Cement clinker | 20-25 | 2-6 | 4-8 | 60-70 | 1-6 | 0.5-2 | 0.5-1 | 0.2-1 | 0-1 |
| Slag | 15-35 | 0.2-5 | 10-30 | 20-35 | 1-10 | 0.5-6 | 0.5-5 | 0.3-1 | 0-3 |
The amount of substance calculation formula:
The molar mass of the quality/material of amount of substance=material
The molecular weight of the percentage ratio/material of amount of substance ratio=material
Eco-cement preparation method of the present invention is as follows:
1, F material part is the mixture that red mud, slag, ironmaking Water Quenching Slag, flyash, titanium ore slag, phosphorus slag, shale, slag, clay, volcanic ash material, bauxite, building waste or one or more materials of waste concrete of adopting the alumina producer of unformed shape or micritization to discharge are formed behind stoicheiometry, add additive, make through grinding.The ratio of components control numerical range of F material:
(mol ratio) [Si]/[Ca]=0.5-1.7 [Si]/[Al]=3.0-1.5
Can adopt the technology of preroasting or not preroasting for above-mentioned shale, clay or bauxite etc., preroasting is with 500-1000 ℃ temperature, and 1-2 hour time carries out.
2, P material part is by one or more mixtures formed in various low-grade bauxites, slag, limestone mine, waste soda residue, phosphorus slag, chemical gypsum, all kinds of cement clinker, carbonate, silicate, aluminate, phosphoric acid salt and the halogen class, add additive, make through grinding.The ratio of components control numerical range of P material:
(mol ratio) [Si]/[Ca]=1.0-0.3 [Si]/[Al]=4.0-2.6
3, D material is as the guiding crystal seed, it synthetic by high reactivity Al (OH)
3, the synthetic at a certain temperature preparation of highly basic, water glass, Tai-Ace S 150, at first be by high reactivity Al (OH)
3, highly basic in reactive tank, carry out chemical combination in the 60-120 ℃ of scope, and then add solid or liquid soluble glass, add the degree of crystallinity 40-70% that Tai-Ace S 150 is adjusted crystal seed at last, be incubated 10-60 hour, temperature is controlled at 40-80 ℃.Each component ratio following (weight percentage):
High reactivity Al (OH)
3: 20-45%
Highly basic: 15-25%
Water glass: 20-40%
Tai-Ace S 150: 10-15%
Additive in above-mentioned F material and the P material mainly is to be used for metering needle to condensation condition and the color and the abrasive of customer requirements, and interpolation mainly is a sodium aluminate when grinding, sodium methyl silicate, calcium saccharate, polyvinyl acetate, active A l (OH)
3, calcium chloride, oxalic dialdehyde, ligninsulfonate, highly basic, quickened lime breast, a kind of in sodium polyphosphate, borate and the trolamine or the mixture that certain is several.Embody in the additive of color matching ion when the P abrasive lapping, arrange in pairs or groups, can make color eco-cements such as brick dust look, pale, grey black, grey according to the element color of primary material.
Preferred size is after the grinding of above-mentioned F material or P material: 200 mesh screen residue 1-10%, specific surface area is 4000cm
2/ g-8000cm
2/ g.The finished product form of above-mentioned F material or P material is solid powdery or wet-milling shape, independent packaging.
Dual mode is adopted in the grinding of above-mentioned F material or P material:
A kind of is the processing conditions that adopts the former Bit Grinding of supplied materials, mainly is after adjusting various available materials according to stoichiometric ratio, goes into mill together and grinds, also can be according to the grinding condition of different material, add additive, enter the mix grinding device after grinding respectively and mix, adopt to grind afterwards earlier and mix.
Another kind is to adopt respectively treated material to add humextant, grinds, and no longer adds abrasive, mainly is to consider the best lapping mode of different material and decide.Humextant mainly is the bigger biological products of water content, as citric acid, jellies material.
Can carry out brokenly in advance during concrete production earlier with jaw crusher to raw material, hang overhead traveling crane with the pawl bucket the more various classification raw materials fortune of material storage yard are fallen former feed bin in each Production Flow Chart.
Each former feed bin links to each other with weighing belt according to the Technology ratio requirement, deliver to ball mill by belt, this moment is according to customer requirements, and the grindability index of going into to grind raw material suitably adds humextant or do not add, but to add additive simultaneously, grind, grind the back material and enter the selection by winnowing hierarchy system, satisfy the requirement of granularity and specific surface like this up to material, best granularity is after the grinding of F material: 200 mesh screen residue 1-10%, specific surface area is (4000-8000) cm
2Behind/the g., be sent to finished bin with belt, encapsulate and put in storage, wet mash adopts barreled or canned.
4, F material or P material can carry out compound earlier with the D material after grinding, form FD material or PD material, do not react, but FD material and P material, FD material and PD material, F material and PD material, F material and P material under the situation that has water to participate in, will produce gelling, hydration reaction takes place, and generates the material with gelling.Adding water is the 25%-65% of F material, P material and D material gross weight.
Packing instructions:
Dry powder material or wet-milling grind materials for F material, P material adopt plastic lining woven bag packing, or carry out cannedly greatly, or carry out barreled.But, all to pack separately, and clearly indicate for F material, P material, FD material, PD material.For the D material, with callable plastics barreled.Can reuse.
The application of eco-cement of the present invention, concrete grammar is as follows:
Eco-cement in use, must follow service regulations with good conditionsi, it is the function that independent F material, P material or D hopper can not be realized gelling material, have only three kinds of material F material, P material and D material or two kinds of compound material of FD material and PD material are mixed mutually, and under the effect that adds combination water, fierce hydration reaction and complicated chemical transformation could take place, provide a kind of environment suitable chemical environment, make the aluminosilicate material of property under the crystal seed guiding of D material, generate gelling material, and finally have all physical propertys of cement.
On concrete the application, with the way of existing ordinary Portland cement is identical, in mortar, concrete preparation process, various separated aggregates can adopt river sand, rubble, piece stone, clay etc. fully, equally also can adopt waste concrete piece, useless brick, tile fragment, glass block or the like.In addition, eco-cement also has good functions of use on aspect the solid sand Gu Ba because it can be directly and soil property class materials such as sand dam, earth dam, grey dam directly react, can realize the fast setting of various dam bodys.
The principle of the invention is as follows:
The explanation of crystal growth basic theories is with a kind of generation of crystalline substance, lean on concrete envrionment temperature, the crystal seed, environmental stress, mother liquid concentration, other factors with system, as: basicity, soluble components, crystallization area or the like, in different environment, also showing different performances with a kind of material, the physics that in the crystalline substance forming process, takes place particularly, chemical transformation, form at lattice, defective has embodied different character on constituting, on horizontal vertical crystal orientation and each crystal orientation, just embodied different properties, when this character is used in varying environment, will show distinguished characteristics in some aspects, the special property material comes to this and forms.
Show special property in the aluminosilicate forming process in some aspects, the present invention is on aluminosilicate crystalline structure research basis, the size of the different coordination particles of discovery salt and different crystalline lattice length, direction, ionic radius, the configuration of energy etc. all is the correlative factor that influences its use properties.
In the aftertreatment use after the aluminosilicate material forms, after must correctly understanding all physicochemical characteristics of this material, could carry out best chemical association proportioning according to its special physicochemical characteristic again, particularly to carry out the combination once more of energy and reconfigure, just can obtain needed effect.
Shale, red mud, phosphorus slag, slag, Water Quenching Slag, slag, slag, flyash, Wingdale, building waste, bauxite, various volcanic ash raw material, coal gangue, clay, mud etc. all are the materials that contains certain aluminosilicate, and suitable amount is all arranged, so just laid good basic substance for further handling.
This aluminosilicate material reconfigures through external energy, and under the guiding of guiding crystal seed, in specific chemical environment, very easily forms the element combinations with high-strength characteristic.
Characteristics of the present invention are as follows:
1, eco-cement is made of jointly several different materials, mainly expect at normal temperatures by in aqueous medium by rich aluminum feedstock (F material) and lean aluminum material (P material) F material, P, hydration reaction takes place, generation has the aluminosilicate material of certain performance, under the guiding of D material, generation has hydraulicity gelatinous material.
2, F material, P material, D material list are solely deposited, and gelatin phenomenon can not take place, and comprise that F material and D material and P material and D material are combined into the FD material and the PD material also can keep stable for a long time, and particularly the PD material can maintain a long-term stability, and does not lump.
3, the F material provides aluminosilicate materials such as necessary element silicon, aluminium element to form necessary elementary composition in eco-cement as rich aluminum feedstock.
4, the P material replenishes the insufficient sial element in the F material except the minor amount of silicon aluminium element is provided, and the coordination ion element of aluminosilicate more is provided simultaneously, as iron, calcium, sodium, potassium, sulphur, lithium, chlorine or the like coordination ion element, reacts with the F material.
5, the D material mainly is when F material and the reaction of P material generation chemical liquid phase, provides a kind of material that guides the typing crystalline structure.
6, D material can be deposited separately, also can expect with F, the P material is combined into the FD material or the PD material, but just with non-compound material different service regulations be arranged in the use.
7, according to different requirements, in F material and D material, also there is colored ion, be mainly used to realize the non-pigment coloring of eco-cement.
Excellent results of the present invention is as follows:
1, the original position that the invention solves the bauxite with rich aluminium element, little crystalline red mud, decrystallized all kinds of water-granulated slags, slag etc. is utilized problem.
2, make full use of flyash proportion F material, the storage problem of the waste of thermoelectric industry is deposited in the stockyard that has solved flyash, various industrial slags.
3, solve various chemical engineering industries trade waste utilize problem.
4, the severe contamination that causes for existing technology of producing cement route finds a practicable terms of settlement.
5, solve the problem of utilizing of various trade wastes, building waste and primary nature sal class material shale, volcanic ash raw material etc.
6, find a kind of production technology of cement product innovation, had the characteristics of ecology, no longer produced secondary pollution, and made full use of refuse.
7, solved the use problem of this eco-cement.
Technical scheme of the present invention is exactly the basic theory that forms according to aluminosilicate, the distinctive physical chemistry of a large amount of human resources such as red mud, slag, ironmaking Water Quenching Slag, flyash, titanium ore slag, phosphorus slag, shale, clay, volcanic ash material, bauxite, building waste, waste concrete, slag, limestone mine, slag is formed, processing through technological process, be made into F material and P material, under the situation of D material as the guiding crystal seed, realize the comprehensive utilization of solid waste, and invented a kind of synthesis technique of ecological class cement simultaneously.
The physical and mechanical property contrast of eco-cement of the present invention and common 425 cement sees the following form 1:
| Sample | Presetting period (h:min) | Final setting time (h:min) | Folding strength (MPa) | Ultimate compression strength (MPa) | ||||
| 3d | 7d | 28d | 3d | 7d | 28d | |||
| Common 425 cement | 3:10 | 5:20 | 4.8 | 5.2 | 6.9 | 16.5 | 28.4 | 44.6 |
| Eco-cement | 2:50 | 4:10 | 5.2 | 6.1 | 7.8 | 24.6 | 35.8 | 53.9 |
The present invention utilizes the physicochemical characteristic of trade waste (as phosphorus slag, slag, red mud, flyash, blast-furnace slag etc. and natural aluminosilicate material shale), select for use excellent chemical to form proportioning, make it reach the materialization requirement of gelling material, by polynary curing technology, synthesize a kind of technology of the ecological gelling material of different grades under certain working conditions with portland cement characteristic.The present invention has realized the comprehensive utilization of solid waste, preparation technology close friend, and the prepared hydraulic cementing materials market space is big, and cost is low, and competitive edge is outstanding, and strategy drive property is strong, and scale and benefit are remarkable, meet characteristics such as environmental requirement.Concrete advantage is as follows:
A. material resistance to corrosion of the present invention is strong, is that Portland cement is unapproachable.
B. the whole process of Sheng Chaning need not be got angry (except the shale processing) substantially, does not discharge carbonic acid gas.
C. the cement of this invention production has fixed sial material, the characteristic of artificial mine, natural earth etc.
D. the gelling characteristic that has of the cement material produced of this invention, its intensity can surpass existing Portland cement under the same case.
E. the various chemical assistants that add during abrasive material make whole material matrix part preparation process not have dust, and are free from environmental pollution.
F. adopt F material, P material, D material etc. polynary synthetic, split packing, the on-the-spot way of using have applicability widely.
G. all raw materials in producing all be red mud, burning boiler slag, smelt iron one or more mixture such as Water Quenching Slag, flyash, titanium ore slag, phosphorus slag, shale, clay, volcanic ash material, bauxite, building waste, waste concrete, slag, limestone mine, slag, really realized turning waste into wealth, realized comprehensive utilization.
H. utilize refuse, no longer produce second environmental pollution, realize the non-harmful cleaning of environment of real meaning, the production model of ecology.
I. eco-cement of the present invention has also significantly reduced the consumption and the waste of land resources.
J. reduced facility investment, be mainly milling system and sorting and packaging system, whole investment and production management expense descend.
K. because of eco-cement significantly reduces, particularly reduced the firing process of existing cement on operation, the cost of raw material is low simultaneously, wide material sources, thereby the production cost than Portland cement has had significantly reduction on comprehensive production cost.
L. the industrial scale of eco-cement of the present invention is changeable, and can be according to productions of founding the factory of raw material, the particular location of using the place, increases on-the-spot ageingly, and the reduction user cost has very big handiness.
(4) description of drawings
Fig. 1 is a F material processing unit schematic flow sheet, wherein A, B ..., D, E ..., the N groove is illustrated on the specific job site, the production trough that disposes by the kind and the processing condition requirement of raw material, represent a series of troughs, be to be used for depositing the various dissimilar raw material that overhead traveling crane ships, generally the size according to original particle size sorts, the A groove is deposited and is given roasting shale or roasting shale not, come last N groove and deposit flyash, and the D groove is to deposit humextant, and the E groove is deposited the chemical additive of F material.
Fig. 2 is a P material processing unit schematic flow sheet, wherein PA, PB ..., PD, PE ..., the PN groove is to be used for depositing the various dissimilar raw material that overhead traveling crane ships, generally the size according to original particle size sorts, as limestone mine, to be placed on the PA groove, and salts substances generally all is placed on last N groove, and the PD groove is a humextant of depositing the P material, and the PE groove is deposited the chemical additive of P material.
Fig. 3 is a D material processing unit schematic flow sheet, wherein, and 1, reinforced, 2, reactive tank, 3, insulation jar, 4, pan tank, 5, barrelling.
(5) embodiment
Further specify the present invention below by embodiment.Wherein the standard of test application is as follows:
GB1346-89: " cement normal consistency water consumption, time of coagulation, the stability method of inspection "
GB/T17671-1999: " Test method for strength of hydraulic cement mortar "
GB1345-91: " the cement fineness method of inspection "
GB8074-87 " Method of determination for specific surface of cement "
Embodiment 1: eco-cement and preparation method, calculate with the weight ratio of primary material:
(1) F material: flyash 15%, water-granulated slag 40%, shale (not roasting) 6.4%, F feed additives: calcium saccharate 0.1%, sodium polyphosphate 0.2%, trolamine 0.3%, the ratio of components of F material: mol ratio [Si]/[Ca]=1.0, [Si]/[Al]=2.25.
Adopt supplied materials original position attrition process, with various available materials, the adding additive is gone into mill together and is ground.Granularity is controlled at 200 mesh screen residues 3%, and specific surface area is 4300cm
2/ g.
(2) P material: slag 5%, lime 13%, phosphorus slag 14.3%, P feed additives: wooden sodium sulfonate 0.2%, quickened lime breast 0.5%, Sodium Tetraborate 0.2%.The ratio of components of P material: mol ratio [Si]/[Ca]=1.0, [Si]/[Al]=2.6.
Above-mentioned each composition adopts supplied materials original position attrition process, and with various available materials, the adding additive is gone into mill together and ground.Granularity is controlled at 200 mesh screen residues 3%, and specific surface area is 4300cm
2/ g.
(3) D material: directed agents 5%, the D material contains admittedly: 78%.
The D material is by high reactivity Al (OH)
3, highly basic, water glass and Tai-Ace S 150 are synthesized into, and at first are by high reactivity Al (OH)
3, highly basic in reactive tank, 100 ℃ are carried out chemical combination, are adding liquid soluble glass then, add the degree of crystallinity 40-70% that Tai-Ace S 150 is adjusted crystal seed at last, are incubated 40 hours, temperature is controlled at 60 ℃.Each composition weight percent is as follows:
High reactivity Al (OH)
3: 35%
Highly basic: 20%
Water glass: 30%
Tai-Ace S 150: 15%.
(4) F material or P material mix with the D material respectively after grinding in advance, form FD material or PD material, do not react, but FD material and P material, FD material and PD material, F material and PD material, F material and P material, adding water is 35% of F material, P material and D material gross weight, and hydration reaction takes place, generate gelling material, have all physical propertys of cement.The weight ratio of F material, P material, D material is as follows: the F material: P material=65: 35, and the D material: (F material+P material)=5: 95.
The cement mortar strength data of relevant eco-cement test see Table 2.
Embodiment 2: eco-cement and preparation method, calculate with the weight ratio of primary material:
(1) F material: flyash 5%, slag 10%, water-granulated slag 39%, shale (roasting) 7%, F feed additives: wooden sodium sulfonate: 0.5%, sodium polyphosphate: 0.1%, polyvinyl acetate 0.4%., the ratio of components of F material: mol ratio [Si]/[Ca]=0.5, [Si]/[Al]=3.0.
Shale in the F material adopts preroasting technology, maturing temperature 800-900 ℃, roasting time 1-2 hour.
Enter the mix grinding device after above-mentioned each composition ground respectively and mix, grind afterwards earlier and mix.
(2) P material: slag 5%, lime 13%, phosphorus slag 13%, P feed additives: sodium polyphosphate 0.1%, active A l (OH)
31%, quickened lime breast 0.9%.Enter the mix grinding device after above-mentioned each composition ground respectively and mix, grind afterwards earlier and mix.
The ratio of components of P material: mol ratio [Si]/[Ca]=0.5, [Si]/[Al]=3.0
The control of F material granularity: 200 mesh screen residues 2%, specific surface area are 5100cm
2/ g;
The control of P material granularity: 200 mesh screen residues 4%, specific surface area are 3900cm
2/ g;
(3) D material: directed agents 5%, the D material contains admittedly: 80%.
The D material is by high reactivity Al (OH)
3, highly basic, water glass and Tai-Ace S 150 are synthesized into, and at first are by high reactivity Al (OH)
3, highly basic in reactive tank, 100 ℃ are carried out chemical combination, are adding liquid soluble glass then, add the degree of crystallinity 40-70% that Tai-Ace S 150 is adjusted crystal seed at last, are incubated 40 hours, temperature is controlled at 60 ℃.Each composition weight percent is as follows:
High reactivity Al (OH)
3: 45%
Highly basic: 25%
Water glass: 20%
Tai-Ace S 150: 10%.
(4) F material, P material, D material are packed respectively, mix by following weight ratio during use,
The F material: P material=65: 35, the D material: (F material+P material)=5: 95.
The cement mortar strength data of relevant eco-cement test see Table 2.
Embodiment 3, cement, calculate with the weight ratio of primary material:
F material: red mud 25%, water-granulated slag 40%, flyash 6%
F feed additives: monocalcium phosphate 3%, sodium aluminate 1%
P material: slag 3%, phosphorus slag 18%
P feed additives: quickened lime breast 0.1%, wooden sodium sulfonate 0.1%, calcium saccharate 0.4%, calcium chloride 1.4%
The control of F material granularity: 200 mesh screen residues 3%, specific surface area are 4300cm
2/ g;
The control of P material granularity: 200 mesh screen residues 4%, specific surface area are 4900cm
2/ g.;
The ratio of components of F material: mol ratio [Si]/[Ca]=1.7, [Si]/[Al]=1.5
The ratio of components of P material: mol ratio [Si]/[Ca]=0.3, [Si]/[Al]=4.0
The D material: directed agents 4%, the D material contains admittedly: 78%.
The D material is by high reactivity Al (OH)
3, highly basic, water glass and Tai-Ace S 150 are synthesized into, and at first are by high reactivity Al (OH)
3, highly basic in reactive tank, 100 ℃ are carried out chemical combination, are adding solid water glass then, add the degree of crystallinity 40-70% that Tai-Ace S 150 is adjusted crystal seed at last, are incubated 40 hours, temperature is controlled at 60 ℃.Each composition weight percent is as follows:
High reactivity Al (OH)
3: 20%
Highly basic: 25%
Water glass: 40%
Tai-Ace S 150: 15%.
All the other preparation methods are all with embodiment 1.
The cement mortar strength data of relevant eco-cement test see Table 2.
Embodiment 4: eco-cement, calculate with the weight ratio of primary material:
F material: red mud 15%, bauxite 10%, water-granulated slag 45%, flyash 2%
F feed additives: monocalcium phosphate: 3%, sodium aluminate: 1%, polyvinyl acetate: 0.1%, wooden sodium sulfonate: 0.1%, sodium polyphosphate: trolamine 0.2%: 0.2%.
P material: slag: 10%, phosphorus slag: 15.1%
P feed additives: quickened lime breast 0.3%, wooden sodium sulfonate 0.1%, calcium saccharate 0.5%, calcium chloride 0.4%, sodium methyl silicate 0.1%, oxalic dialdehyde 0.1%, wooden calcium sulfonate 0.2%, Sodium Tetraborate 0.2%;
The control of F material granularity: 200 mesh screen residues 1%, specific surface area are 5900cm
2/ g.;
The control of P material granularity: 200 mesh screen residues 4%, specific surface area are 4900cm
2/ g;
The D material: directed agents 10%, the D material contains admittedly: 78%.The D material is synthetic as embodiment 1.
The cement mortar strength data of relevant eco-cement test see Table 2.
The physical and mechanical property of table 2 eco-cement
| Specimen coding | Presetting period (h:min) | Final setting time (h:min) | Stability | Color | Folding strength (MPa) | Ultimate compression strength (MPa) | ||||
| 3d | 7d | 28d | 3d | 7d | 28d | |||||
| Embodiment 1 | 2:30 | 4:15 | Well | Ash | 4.9 | 5.2 | 6.1 | 19.2 | 28.4 | 48.5 |
| Embodiment 2 | 2:15 | 3:55 | Well | Greyish white | 4.2 | 4.9 | 5.9 | 20.8 | 31.9 | 51.4 |
| Embodiment 3 | 1:55 | 4:04 | Well | Ash | 3.8 | 5.1 | 7.8 | 23.5 | 34.2 | 55.2 |
| Embodiment 4 | 2:25 | 4:13 | Well | Ash | 4.1 | 5.9 | 7.4 | 21.8 | 33.6 | 54.1 |
Embodiment 5: eco-cement, calculate with the weight ratio of primary material:
F material: titanium ore slag 15%, flyash 10%, slag 34%, red mud 7%, shale 10%
F feed additives: sodium aluminate 1%, active A l (OH)
3: 2%, calcium chloride 1%, wooden sodium sulfonate 0.1%, sodium polyphosphate 0.1%;
The P material: slag 2%, alkaline residue: 5%, phosphorus slag 4.1%
P feed additives: sodium methyl silicate 0.2%, calcium saccharate 0.1%, polyvinyl acetate 0.1%, oxalic dialdehyde 0.2%, wooden calcium sulfonate 0.1%, sodium hydroxide 0.1%, quickened lime breast 0.1%
The control of F material granularity: 200 mesh screen residues 4%, specific surface area are 4200cm
2/ g;
The control of P material granularity: 200 mesh screen residues 2%, specific surface area are 4900cm
2/ g;
The D material: directed agents 3.8%, the D material contains admittedly: 69%.The D material is synthetic as embodiment 1.
The cement mortar strength data of relevant cement testing see Table 3.
Embodiment 6: cement, calculate with the weight ratio of primary material:
F material: flyash 5%, ironmaking Water Quenching Slag 35%, titanium ore slag 10%, shale 10%, bauxite 5%
F feed additives: wooden sodium sulfonate 0.5%, sodium polyphosphate 0.1%, polyvinyl acetate 0.1%, trolamine 0.3%, monocalcium phosphate 1%;
P material: slag 7%, Wingdale 9.9%, cement clinker 10%,
The P feed additives: sodium-chlor 0.5%,, sodium aluminate 0.5%, monocalcium phosphate 0.1%, sodium polyphosphate 0.1%, active A l (OH)
31%;
The control of F material granularity: 200 mesh screen residues 3%, specific surface area are 4500cm
2/ g;
The control of P material granularity: 200 mesh screen residues 4%, specific surface area are 4300cm
2/ g;
The D material: directed agents 2.9%, the D material contains admittedly: 75%.The D material is synthetic as embodiment 1.
The cement mortar strength data of relevant eco-cement test see Table 3.
Embodiment 7: eco-cement, calculate with the weight ratio of primary material:
F material: ironmaking Water Quenching Slag 15%, flyash 25%, titanium ore slag 10%, clay 5%, low-grade bauxite 5%
F feed additives: sodium aluminate 3%, active A l (OH)
31%, wooden sodium sulfonate 0.2%, sodium polyphosphate 0.3%, trolamine 0.2%;
P material: slag 10%, Wingdale: 5%, phosphorus slag 10%, cement clinker 3%,
The P feed additives: sodium methyl silicate 0.3%, calcium saccharate: 0.2%, calcium chloride: 0.4, salt of wormwood: 0.5%, sodium polyphosphate: Sodium Tetraborate 0.1%: 0.4%;
The control of F material granularity: 200 mesh screen residues 1%, specific surface area are 6000cm
2/ g;
The control of P material granularity: 200 mesh screen residues 3%, specific surface area are 4300cm
2/ g;
The D material: directed agents 5.4%, the D material contains admittedly: 70%.The D material is synthetic as embodiment 1.
The cement mortar strength data of relevant eco-cement test see Table 3.
Embodiment 8: eco-cement, calculate with the weight ratio of primary material:
The F material: bauxite 5%, water-granulated slag 35%, flyash 10%, shale (roasting) 5%, cement clinker 3%,
F feed additives: monocalcium phosphate 3%, sodium aluminate 1%, polyvinyl acetate 0.5%, wooden sodium sulfonate 0.1%, sodium polyphosphate 0.2%, trolamine 0.2%;
The P material: slag 10%, slag 8.4%, phosphorus slag 12.9%,
P feed additives: quickened lime breast 1%, wooden sodium sulfonate 0.1%, calcium chloride 0.4%, sodium hydroxide 0.5%, sodium methyl silicate 0.1%, oxalic dialdehyde 0.1%, wooden calcium sulfonate 0.2%, Sodium Tetraborate 0.2%;
The control of F material granularity: 200 mesh screen residues 2%, specific surface area are 5400cm
2/ g;
The control of P material granularity: 200 mesh screen residues 2%, specific surface area are 5200cm
2/ g;
The D material: directed agents 3.6%, the D material contains admittedly: 70%.The D material is synthetic as embodiment 1.
The cement mortar strength data of relevant eco-cement test see Table 3.
The physical and mechanical property of table 3 eco-cement
| Specimen coding | Presetting period (h:min) | Final setting time (h:min) | Stability | Color | Folding strength (MPa) | Ultimate compression strength (MPa) | ||||
| 3d | 7d | 28d | 3d | 7d | 28d | |||||
| Embodiment 5 | 3:30 | 5:15 | Well | Brick dust | 4.9 | 5.2 | 7.2 | 25.1 | 38.4 | 68.5 |
| Embodiment 6 | 2:35 | 4:45 | Well | Greyish white | 4.6 | 6.9 | 8.9 | 26.5 | 36.2 | 72.2 |
| Embodiment 7 | 2:46 | 3:58 | Well | The China ink ash | 3.9 | 5.6 | 6.8 | 21.5 | 29.9 | 60.5 |
| Embodiment 8 | 2:15 | 4:24 | Well | Ash | 4.8 | 6.1 | 7.6 | 26.4 | 39.1 | 76.3 |
Claims (8)
1. eco-cement is characterized in that comprising rich aluminum feedstock F material, lean aluminum material P material and guiding crystal seed D material, wherein,
F material is a mixture of selecting for use one or more materials in red mud, slag, ironmaking Water Quenching Slag, flyash, titanium ore slag, phosphorus slag, shale, slag, clay, volcanic ash material, bauxite, building waste and the waste concrete that the alumina producer of unformed shape or micritization discharges to form, batching mol ratio [Si]/[Ca]=0.5-1.7, [Si]/[Al]=3.0-1.5;
The P material is a mixture of selecting one or more compositions in bauxite, slag, limestone mine, waste soda residue, phosphorus slag, chemical gypsum, cement clinker, carbonate, silicate, aluminate, phosphoric acid salt and the halogen class for use, batching mol ratio [Si]/[Ca]=1.0-0.3, [Si]/[Al]=4.0-2.6
Above-mentioned phosphorus slag and/or slag are not placed in F material and the P material simultaneously;
The D material is by high reactivity Al (OH)
3, highly basic, water glass and Tai-Ace S 150 is synthesized into; Synthesizing of described D material at first is by high reactivity Al (OH)
3, highly basic in reactive tank, carry out chemical combination in the 60-120 ℃ of scope, and then add solid or liquid soluble glass, add the degree of crystallinity 40-70% that Tai-Ace S 150 is adjusted crystal seed at last, be incubated 10-60 hour, temperature is controlled at 40-80 ℃, each composition weight percent is as follows:
High reactivity Al (OH)
3: 20-45%
Highly basic: 15-25%
Water glass: 20-40%
Tai-Ace S 150: 10-15%;
The weight ratio of F material, P material, D material is as follows:
The F material: P material=10-99: 1-80,
D material: (F material+P material)=1-30: 70-99.
2. eco-cement as claimed in claim 1 is characterized in that described F material: P material=60-89: 11-40, weight ratio.
3. eco-cement as claimed in claim 1 is characterized in that described D material: (F material+P material)=1-10: 90-99, weight ratio.
4. eco-cement as claimed in claim 1 is characterized in that described F material or P expect the weight percent 0.1-45% of water content.
5. eco-cement as claimed in claim 1 is characterized in that described F material or P material have additive, additive when grinding be sodium aluminate, sodium methyl silicate, calcium saccharate, polyvinyl acetate, active A l (OH)
3, calcium chloride, oxalic dialdehyde, in ligninsulfonate, highly basic, quickened lime breast, sodium polyphosphate, borate and the trolamine one or more.
6. eco-cement as claimed in claim 5 is characterized in that described F material or P feed additives add-on account for the weight percent 0.5-10% of F material or P material.
7. the preparation method of claim 1 or 5 described eco-cements is characterized in that step is as follows:
(1) F material part is the mixture that adopts one or more materials in red mud, slag, ironmaking Water Quenching Slag, flyash, titanium ore slag, phosphorus slag, shale, slag, clay, volcanic ash material, bauxite, building waste and the waste concrete that the alumina producer of unformed shape or micritization discharges to form behind stoicheiometry, perhaps add additive, make the ratio of components control numerical range of F material through grinding:
Mol ratio [Si]/[Ca]=0.5-1.7 [Si]/[Al]=3.0-1.5
For the technology of above-mentioned shale, clay or bauxite employing preroasting or not preroasting, pre-calcination temperature 500-1000 ℃, time 1-2 hour;
(2) P material part is by one or more mixtures formed in various low-grade bauxites, slag, limestone mine, waste soda residue, phosphorus slag, chemical gypsum, all kinds of cement clinker, carbonate, silicate, aluminate, phosphoric acid salt and the halogen class, perhaps add additive, make the ratio of components control numerical range mol ratio of P material through grinding:
[Si]/[Ca]＝1.0-0.3 [Si]/[Al]＝4.0-2.6；
(3) D material guiding crystal seed is synthetic, at first is by high reactivity Al (OH)
3, highly basic in reactive tank, carry out chemical combination in the 60-120 ℃ of scope, and then add solid or liquid soluble glass, add Tai-Ace S 150 at last and adjust the degree of crystallinity 40-70% of crystal seed, be incubated 10-60 hour, temperature is controlled at 40-80C, each component ratio is as follows, weight percentage:
High reactivity Al (OH)
3: 20-45%
Highly basic: 15-25%
Water glass: 20-40%
Tai-Ace S 150: 10-15%;
(4) F material or P material carry out compound earlier with the D material after grinding, form FD material or PD material, do not react, but FD material and P material, FD material and PD material, F material and PD material, F material and P material are under the situation that has water to participate in, will produce gelling, hydration reaction takes place, generate the material with gelling, adding water is the 25%-65% of F material, P material and D material gross weight.
8. the preparation method of eco-cement as claimed in claim 7 is characterized in that, one of following dual mode is adopted in the grinding of described F material or P material:
(1) processing conditions of the former Bit Grinding of employing supplied materials mainly is after adjusting various materials according to described stoichiometric ratio, goes into mill together and grinds, or according to the grinding condition of different material, add additive, enter the mix grinding device after grinding respectively and mix, adopt to grind afterwards earlier and mix;
(2) adopt respectively treated material to add humextant, grind, humextant is citric acid or jelly.
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|---|---|---|---|
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| CN107382102A (en) * | 2017-08-14 | 2017-11-24 | 昌都龙者高新材料股份有限公司 | Eco-cement for highlands |
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| WO2024187013A1 (en) * | 2023-03-07 | 2024-09-12 | University Of Virginia Patent Foundation | Concrete compositions and methods of making and using concrete compositions |
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| CN107382102A (en) * | 2017-08-14 | 2017-11-24 | 昌都龙者高新材料股份有限公司 | Eco-cement for highlands |
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