CN1055277C - Prodn. of composite portland cement by utilizing industrial waste residue - Google Patents

Prodn. of composite portland cement by utilizing industrial waste residue Download PDF

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CN1055277C
CN1055277C CN98112275A CN98112275A CN1055277C CN 1055277 C CN1055277 C CN 1055277C CN 98112275 A CN98112275 A CN 98112275A CN 98112275 A CN98112275 A CN 98112275A CN 1055277 C CN1055277 C CN 1055277C
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cement
portland cement
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composite
composite portland
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CN1213654A (en
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李潜
刘党生
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QIFU CEMENT PLANT MIANZHU CITY SICHUAN PROV
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QIFU CEMENT PLANT MIANZHU CITY SICHUAN PROV
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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
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/02—Portland cement
    • 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)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The present invention relates to composite Portland cement produced from industrial waste. A raw material is compounded according to a high saturation ratio, more than 30% of admixtures composed of phosphorous slag, phosphorous slag, phosphogypsum, fly ash and limestone are added in calcined clinker, and thus, a product is processed by the processes of homogenization, crushing, milling, etc. The strength of phosphorous slag active materials is thoroughly activated by a technology, and thus, the cement has the advantages of high cement early strength, fast increase, folding resistance of produced cement products and high anti-compression strength. The product not only is consistent with a national standard GB12958-91 by the checking of a quality testing department, but also has a physicochemical index which is superior to the national standard.

Description

The composite Portland cement and the preparation method that utilize industrial residue to produce
The present invention relates to utilize the main composite material of Industry Waste slag as cement through a kind of composite Portland cement of processing, this product is used for the construction such as prefabricated components, highway, bridge, culvert, is specially adapted to water conservancy construction.
Along with the development of market economy, the continuous increase of phosphorous chemical industry enterprise, will discharge a large amount of industrial residues every year, as not administering, then can pollute to socio-ecological environment, and land occupation, the development of restriction enterprise. How to turn waste into wealth: environmental contamination reduction, effectively utilize industrial residue, the exploitation building resource reduces production costs, and this is the problem of for many years consistent investigation of many manufacture of cement producers. In existing comprehensive silicon silicon salt cement production technology, have and utilize industrial phosphorus slag to be added in the clinker as composite material. But, owing to close a large amount of phosphorus pentoxides in the phosphorus slag, because phosphorus pentoxide destroys strength of cement, delays cement setting time, so the phosphorus slag blended amount is few, only account for the 5-15% of cement raw material gross weight, and in processing, also need phosphorus slag is anticipated, be about to the harmful substance phosphorus pentoxide (P20 in the phosphorus slag. ) with lime or alkali except abandoning because except abandoning technical deficiency, cause that cement setting time is long, early strength is low, the stability qualified time is long etc., the specification requirement so cement products can not be up to state standards. " phosphorus ore slag comprehensive silicon changes the research of salt cement performance " document in 93 years the 5th phases " cement, lime ", reported a kind of take clinker, slag, phosphorus slag, gypsum, exciting agent as raw material, cooperate the phosphorus ore slag composite silicate cement that processes through operations such as grindings in suitable ratio. Although the composite material of this cement has also utilized industrial residue, in batching, must add exciting agent, cost up, production technology link are increased, so can not apply.
The applicant is for above-mentioned technical problem, think that calcium silicates mineral and wherein harmful substance are the key factors that the cement physical and chemical index is exerted an influence, the phosphorus slag that utilizes industrial residue is how to activate wherein calcium silicates mineral intrinsic strength as the key of cement admixture. For this reason, the applicant inquire into to activate the feasible way of phosphorus slag for many years repeatedly, through reaching 7 years concentrate on studies, repetition test, finally successfully develops and activate phosphorus slag intensity, improves complex cement quality new technology. This technology is a kind of composite Portland cement (name of product is " beautiful good fortune board " composite Portland cement) that effectively utilizes industrial residue to produce. Both early strength is high, be up to state standards setting time for this cement, later strength increase fast, and reduce the cost of raw material, production technology remains unchanged substantially.
The objective of the invention is to realize by this way: adopt the high saturation ratio scheme, improve in the grog and remain calcium oxide content, harmful substance phosphorus in the utilization harmful substance free calcium precipitation phosphorus slag wherein, fluorine etc., fully activate the intensity of reactivity of phosphor slag thing, use the machine producing clinker in vertical kiln, cooperate many blending of phosphorus slag condensation material to produce composite Portland cement. It is to prepare burden by high saturation ratio with the raw material that ore, anthracite, clay, iron powder form, and admixture processes product through operations such as homogenizing, fragmentation, grindings again with the composite material that phosphorus slag, gypsum, flyash, lime stone were formed in the grog after calcining.
In the grog after calcining directly the admixture percentage by weight greater than 30% with composite material that phosphorus slag, flyash, lime stone, ardealite were formed.
Grog and composite material proportioning by weight percentage is: Portland clinker 50-70%, phosphorus slag 12-35%, flyash 5-15%, lime stone 3-5%, ardealite 1-5%; Preferred proportioning is: Portland clinker 65%, phosphorus slag 20%, flyash 8%, lime stone 3%, ardealite 4%.
Composite material behind 300-350 ℃ of hyperthermia drying admixture in grog.
Used phosphorus slag meets standard GB/T 6645-86, GB12957-91 " the granulation electric furnace phosphoric slag that is used for cement " specification requirement in batching; Flyash meets standard GB/T 1596, GB12957-91 " flyash that is used for cement and concrete " requirement; Lime stone requires alundum (Al2O3)≤2.5%.
Adopt technique scheme, suitably adjust the proportioning of high saturation ratio and grog and the composite material of raw material, can produce the composite Portland cement of different labels. The present invention is owing to adopted high saturation ratio scheme (calcium oxide is by the ratio K H of acidic materials combination without repetition 〉=0.9), utilize the harmful substance phosphorus pentoxide in the free calcium precipitation phosphorus slag of high-load in its grog, fully activate the intensity of reactivity of phosphor slag thing, thereby can improve the addition content of phosphorus slag; In addition, owing to contain a large amount of indefiniteness silicon in the flyash, can be used as on the one hand packing material, utilize its activity on the other hand, also utilize simultaneously alundum (Al2O3) wherein to be combined with gypsum again, form strong material entringite morning of cement. Therefore, adjust Clinker Composition and composite material proportioning, do not need composite material is carried out preliminary treatment, replace the high value composite material with the low value composite material, (two materials are through Experimental Comparison: effect is identical with ardealite instead for the set retarder dihydrate gypsum; Do the armored concrete test, without corrosion phenomenon), the present invention takes full advantage of native industry three wastes resource (being phosphorus slag, flyash, ardealite) and has reduced the pollution of waste residue to environment, turns waste into wealth, its economic benefit and social benefit are very remarkable, and ecological benefits are better. This product reduces more than 20 yuan/ton of cost, saves electricity more than 10% than ordinary cement, the product sampling is through Sichuan Province's Deyang City local cement quality monitoring testing station, the cement product quality supervision and inspection station check of Sichuan Province Bureau of Technical Supervision, the composite Portland cement that meets standard GB/T 12958-91 requires (seeing Appendix 1), and physical and chemical index also is better than national standard. Cement early strength of the present invention is high, and later strength increases fast, and the anti-folding of the cement products of production, compression strength are high, and applied widely, plasticity good, moderate, promotional value is large.
Below the present invention is elaborated.
Accompanying drawing 1 is rolled into a ball for technological process signal of the present invention.
Embodiment one: produce 1000Kg cement, the raw material proportioning is: grog 650kg, phosphorus slag 200kg, flyash 80kg, lime stone 30Kg, ardealite 40kg. Its " batching chemical analysis " is referring to table one.
The production method of composite Portland cement of the present invention is to adopt the technique (referring to accompanying drawing 1) of existing production cement. Through raw meal proportioning → fragmentation → raw material silo → raw material abrasive dust → storehouse, raw material garden → machine shaft kiln → clinker warehouse → batching → fragmentation → grog storehouse → cement abrasive dust → cement garden storehouse → homogenizing → packing → check → qualified finished product. Wherein: after the raw material that prepare are carried out artificial homogenizing by the neat water 11-93 of Q/ requirement, through jaw crusher and twice fragmentation of fine crusher, granularity requirements≤20mm; To contain the coal chemistry complete analysis by the neat water 01-93 of GB176-87, Q/, the neat water 11-93 of Q/ requirement behind the raw material abrasive dust of raw material silo; Raw material enter mechanical shaft kiln burning ripe material (calcining heat 1250-1450 ℃, about 20 minutes time), grog is carried out the chemical analysis test by GB176-87, GB177-85, GB1346-89, with the composite material that directly adds in the grog after the calcining by said ratio; Grog and composite material are put jaw crusher carry out fragmentation (granularity≤20mm); Grog and the composite material cement material after mixing is carried out grinding with ball mill, and cement flour is carried out stability, intensity, fineness complete chemical analysis by GB176-87, GB177-85, GB1346-89; Cement is packed by every bag 50Kg (permission-1kg error). Product colour is iron black look. This product " measure of merit parameter " sees Table seven, and product is better than the composite Portland cement technical indicator of standard GB/T 12958-91 regulation.
Embodiment two: produce 1000Kg cement, the raw material proportioning is: grog 675kg, phosphorus slag 150kg, flyash 110kg, lime stone 30kg, ardealite 35kg. Its " batching chemical analysis " is referring to table two.
The method of producing cement is to adopt the technique (referring to accompanying drawing 1) of existing production composite Portland cement. Production technology is with embodiment one. This product " measure of merit parameter " sees Table seven, the be up to state standards composite Portland cement technical indicator of GB12958--91 regulation of product.
Embodiment three: produce 1000Kg cement, the raw material proportioning is: grog 653kg, phosphorus slag 135kg, flyash 144kg, lime stone 32Kg, ardealite 36kg. Its " batching chemical analysis " is referring to table three.
The method of producing cement is to adopt the technique (referring to accompanying drawing 1) of existing production composite Portland cement. The manufacturing procedure step is still with embodiment one. This product " measure of merit parameter " sees Table seven, and product meets the composite Portland cement technical indicator of standard GB/T 12958-91 regulations.
Embodiment four: produce 1000Kg cement, the raw material proportioning is: grog 540kg, phosphorus slag 264kg, flyash 105kg, lime stone 46kg, ardealite 45kg. Its " batching chemical analysis " is referring to table four.
The method of producing cement is to adopt the technique (referring to accompanying drawing 1) of existing production composite Portland cement. The manufacturing procedure step is with embodiment one. This product " measure of merit parameter " sees Table seven, and product is better than the composite Portland cement technical indicator of standard GB/T 12958-91 regulations.
Embodiment five: produce 1000Kg cement, the raw material proportioning is: grog 505kg, phosphorus slag 350kg, flyash 60kg, lime stone 40Kg, ardealite 45kg. Its " batching chemical analysis " is referring to table five.
The method of producing cement is to adopt the technique (referring to accompanying drawing 1) of existing production composite Portland cement. The manufacturing procedure step is with embodiment one. This product " measure of merit parameter " sees Table seven, and product meets the composite Portland cement technical indicator of standard GB/T 12958-91 regulations.
The raw material that the present invention forms with ore, anthracite, clay, iron powder material are pressed the high saturation ratio batching, grog through the production of machine shaft kiln carries out the chemical analysis quantitative measurement by GB176-87, GB177-85, GB1346-89, listed one group of " grog chemical analysis " of surveying at table six, long by this " grog chemical analysis " production Portland cement qualified cycle of stability, production composite Portland cement of the present invention goes out to grind the stability qualification rate and reaches more than 95%.
The ardealite of above-described embodiment also available dihydrate gypsum replaces, but cost increases to some extent.
In the above-described embodiments, the composite material of fusion can add behind 300-350 ℃ of hyperthermia drying again in the grog.
In showing below, the chemical molecular formula of each chemical name:
Loss on ignition (Loss) silica (SiO2) di-iron trioxide (Fe2O 3) alundum (Al2O3) (Al2O 3) calcium oxide (CaO) magnesia (MgO) sulfur trioxide (SO3) free calcium oxide (F-CaO) phosphorus pentoxide (P2O 5)
Saturation ratio KH of the present invention calculates by following formula: KH = CaO - 0 . 35 F e 2 O 4 - 1 . 65 A l 2 O 3 2 . 8 Si O 2 Annex 1: 1 part of table one batching of cement test report chemical analysis (%)
Title Loss   SiO 2  Fe 2O 3  Al 2O 3  CaO  MgO   SO 3  F-CaO   KH
Clinker phosphorous residue coal ash phosphorus plaster stone lime stone 1.73 -0.2 15.16 21.98 42.2   19.11   36.84   34.54   2.36   2.32   5.13   1.65   17.85   1.02   0.26   6.82   6.27   22.74   0.98   0.89   63.80   47.89   6.94   31.68   53.30  1.83  0.67  1.37  0.45  0.72  1.82  41.26 6.29 0.948
Table two batching chemical analysis (%)
Title   Loss    SiO 2   Fe 2O 3  Al 2O 3  CaO  MgO  SO 3  F-CaO   KH
Clinker phosphorous residue fly ash-lime stone ardealite   1.31   -0.30   20.04   42.54   18.47   19.60   43.34   45.13   1.08   4.57   0.62   7.96   0.24   0.54   6.34   4.62   20.19   0.44   1.20   63.08   45.74   2.49   53.76   30.06   1.90   2.63   1.60   0.70   1.63   2.03   40.50   4.26   0.93
Table three batching chemical composition (%)
Title Loss  SiO 2  Fe 2O 3  Al 2O 3    CaO  MgO  SO 3 F-CaO     P 2O 5   KH
Clinker phosphorous residue fly ash-lime stone ardealite  0.82  -0.19  20.12  42.08  22.99  19.30  42.16  46.22  0.72  0.52  4.80  1.16  6.44  0.35  0.92  6.18  4.66  17.44  0.67  1.15  63.92  46.46  3.02  53.62  28.86  1.75  1.84  1.82  1.29  1.40  2.09  41.78  4.14     0.90  0.963
Table four batching chemical analysis (%)
Title Loss  SiO 2  Fe 2O 3  Al 2O 3     CaO  MgO  SO 3  F-CaO  P 2O 5   KH
Clinker phosphorous residue fly ash-lime stone ardealite  0.80  -1.54  13.62  42.59  10.76  19.10  38.18  30.41  0.69  3.29  5.90  4.19  18.81  0.27  1.30  6.77  6.17  24.02  0.69  1.04  63.91  44.91  8.64  53.69  34.14  1.91  1.97  2.71  0.83  1.12  1.89  46.76  5.30  2.04  0.35  0.953
Table five batching chemical analysis (%)
Title    Loss  SiO 2  Fe 2O 3  Al 2O 3     CaO    MgO    SO 3  F-CaO    P 2O 5    KH
Clinker phosphorous residue fly ash-lime stone ardealite   0.92   -0.20   17.54   42.90   19.28   41.52   50.42   0.89   4.96   1.12   6.75   0.40   5.92   5.27   17.46   0.76   64.0   47.76   3.39   53.67   1.79   1.48   1.13   0.74   2.18   42.92   4.57   2.26   0.972
Table six grog chemical analysis (%)
Loss   SiO 2   Al 2O 3     Fe 2O 3     CaO     MgO      SO 3      F-CaO     kH
0.86 0.78 0.85 0.54 0.98 ≤1   19.48   19.66   19.34   19.39   19.09   19.0±   6.22   6.20   6.22   6.31   6.29   6.20±     4.67     4.60     4.56     5.03     5.16     4.60±     63.64     63.44     63.84     63.38     63.03     63.00±     1.85     1.84     1.84     1.86     1.94     ≤5.0     1.77     2.06     2.00     1.98     1.72     2.00±     3.84     4.09     4.26     4.02     4.38     4.00±     0.949     0.945     0.960     0.943     0.951     0.962
Table seven measure of merit parameter
Embodiment Anti-folding (MPa) Resistance to compression (MPa) Initial set final set   SO 3(％) Stability
3 days 28 days 3 days 28 days (hour: minute) (hour: minute)
Embodiment one embodiment two embodiment three embodiment four embodiment five   6.3   4.4   6.2   5.0   3.5   10.8   7.0   8.6   9.7   9.1   36.4   28.0   34.0   26.2   18.7  70.2  49.4  59.0  64.0  50.4   1：54   5：29     3.28     2.95     2.99     2.80     2.67 Qualified qualified

Claims (3)

1 one kinds of composite Portland cements that utilize industrial residue to produce is characterized in that described cement forms (by weight percentage) by following component:
Portland clinker 50-70%
Phosphorus slag 12-35%
Flyash 5-15%
Lime stone 3-5%
Ardealite 1-5%
2. composite Portland cement as claimed in claim 1, it is characterized in that: described cement forms (by weight percentage) by following component:
Portland clinker 65%
Phosphorus slag 20%
Flyash 8%
Lime stone 3%
Ardealite 4%
3. the preparation method of composite Portland cement as claimed in claim 1 is characterized in that: will be incorporated in the Portland clinker behind 300～350 ℃ of hyperthermia dryings by the compound that phosphorus slag, flyash, lime stone, ardealite form.
CN98112275A 1998-10-01 1998-10-01 Prodn. of composite portland cement by utilizing industrial waste residue Expired - Fee Related CN1055277C (en)

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CN1296306C (en) * 2005-05-24 2007-01-24 武汉理工大学 Process for fast baking early strength silicate cement clinker
CN100387539C (en) * 2005-12-30 2008-05-14 绵竹市齐福水泥厂 Composite portland cement produced by full utilization of industrial waste slag
CN102173609A (en) * 2011-01-04 2011-09-07 段力为 Cement and preparation method thereof
CN102745919A (en) * 2012-06-18 2012-10-24 福建省新创化建科技有限公司 Preparation method of tailing micropowder portland cement
CN103241967A (en) * 2013-05-16 2013-08-14 河南理工大学 Calcine-free slag material based cement
CN104724967A (en) * 2013-12-20 2015-06-24 南京中联水泥有限公司 Method for prolonging setting time of cement
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CN105293968A (en) * 2015-11-30 2016-02-03 马鞍山泓宇材料科技有限公司 Phosphorus slag compound modifying agent
CN105948608A (en) * 2016-04-16 2016-09-21 南通蛇类治疗研究所 Ecologically healthy environment-friendly cement
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN85100571A (en) * 1985-04-01 1986-03-10 南京工学院 Phosphoric slag cement
CN1033373A (en) * 1987-12-02 1989-06-14 水利电力部长江流域规划办公室长江科学院 Low clinker phosphorous residue cement and processing method

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN85100571A (en) * 1985-04-01 1986-03-10 南京工学院 Phosphoric slag cement
CN1033373A (en) * 1987-12-02 1989-06-14 水利电力部长江流域规划办公室长江科学院 Low clinker phosphorous residue cement and processing method

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