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WO1986005773A1 - Utilisation de la poussiere des fours a ciment et des boues rouges pour produire du ciment hydraulique - Google Patents

Utilisation de la poussiere des fours a ciment et des boues rouges pour produire du ciment hydraulique Download PDF

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Publication number
WO1986005773A1
WO1986005773A1 PCT/US1986/000671 US8600671W WO8605773A1 WO 1986005773 A1 WO1986005773 A1 WO 1986005773A1 US 8600671 W US8600671 W US 8600671W WO 8605773 A1 WO8605773 A1 WO 8605773A1
Authority
WO
WIPO (PCT)
Prior art keywords
cement
iron content
high iron
red mud
clinker
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1986/000671
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English (en)
Inventor
Hassan Kunbargi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of California Berkeley
University of California San Diego UCSD
Original Assignee
University of California Berkeley
University of California San Diego UCSD
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of California Berkeley, University of California San Diego UCSD filed Critical University of California Berkeley
Publication of WO1986005773A1 publication Critical patent/WO1986005773A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C04B7/22—Iron ore cements ; Iron rich cements, e.g. Ferrari cements, Kühl 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
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • 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

Definitions

  • This invention relates to a method of making a special form of cement, differing significantly from Portland cement, and having a relatively high iron content, and to the resultant cement and concrete.
  • the present invention involves, as an important aspect thereof, the making of cement from two materials which are available in very large quantities as waste byproducts of (1) the cement industry and (2) the aluminum industry. More specifically, these waste materials are Cement Kiln Dust, better known as CKD, and the "Red Mud” which remains as a residue in the course of the process of extracting aluminum from the aluminum-containing ore, bauxite.
  • Cement Kiln Dust better known as CKD
  • Red Mud which remains as a residue in the course of the process of extracting aluminum from the aluminum-containing ore, bauxite.
  • Cement such as Portland cement is the product of reaction at high temperature (in the order of 1400 degrees C. to 1600 degrees C.) of (a) an argillaceous material such as clay, containing substantial proportions of silicon oxide, or silica, and aluminum oxide or alumina, and (2) a calcareous material such as lime, which is formed principally of calcium oxide.
  • an argillaceous material such as clay, containing substantial proportions of silicon oxide, or silica, and aluminum oxide or alumina
  • a calcareous material such as lime, which is formed principally of calcium oxide.
  • cement is added to the Portland cement, and normally gravel is also added and of course a proper proportion of water.
  • the resultant Portland concrete takes a substantial period of time to set up, and reaches a substantial level of its final strength in about a month.
  • cement is mixed directly with water, it may be referred to as a paste; and when it is mixed with sand but not gravel, it may be referred to as mortar.
  • the collected CKD may be fed back into the process with the pulversized raw materials.
  • the sodium and potassium alkali content of the collected CKD tends to build up, in view of the lower melting point of sodium and potassium oxides; and it creates a problem when this alkali content, in terms of sodium and/or potassium alkali oxides , exceeds about 0.6 percent or one percent, because of the resultant lowering of the fusion temperature of the material being processed. This reduces the thickness of the layer of material coating and protecting the refractory lining of the kiln.
  • the higher percentages of sodium and potassium alkalis in the Portland cement being processed results in the formation of free lime, which may eventually cause concrete to crack, because it expands in the presence of water.
  • Bauxite is the ore which is most widely used as a source of aluminum.
  • Aluminum oxide is present in bauxite in an amount equal to about 60 percent or 65 percent.
  • As one step in the processes for extracting aluminum oxide from bauxite some of the aluminum oxide is leached from the crushed bauxite ore, with hydrochloric acid and sodium chloride often being used, and the solid residue from the leaching step or steps is known as "Red Mud", or “Brown Mud” , with different sources of aluminum ore and slightly different processes giving a residue of somewhat different colors.
  • the phrase "Red Mud” with initial capital letters will refer to this type of by-product material, whether red in color or brown.
  • the production of Red Mud is more than 5,000,000 tons per year; and it has been estimated that approximately ninety million tons have been accumulated in settling ponds.
  • an excellent cement may be formed from the two waste products, (1) cement kiln dust, CKD, and (2) "Red Mud", combined with the addition of (3) sulfur containing material, such as gypsum, calcium sulfate.
  • sulfur containing material such as gypsum, calcium sulfate.
  • the alumina, or aluminum oxide content of the Red Mud is low, it may be supplemented by the addition of more (4) alumina or aluminum oxide.
  • some (5) calcareous material such as lime may be added to the mixture.
  • raw materials are finely divided and intimately mixed, and thereafter may be processed in a rotary kiln or in a comparable heating process at somewhat lower temperatures, such as 1250 degrees C. to 1350 degrees C., with no need to exceed 1400 degrees C.
  • the resulting clinker may be pulverized as in the case of conventional Portland cement.
  • the resultant concrete has excellent strength, with its compressive strength being greater than concrete made from Portland cement, and in some cases comparative compressive strength tests showed the new concrete to be more than fifty percent (50%) stronger than Portland concrete.
  • Additional advantages of the new cement include the reduced manufacturing cost resulting from the lower temperature of fusion, the slightly lighter weight of the new cement, and the very rapid setting time of the new cement. It is also believed that the higher iron content of the new cement provides improved bonding with the steel reinforcing widely used in concrete, and accordingly increases the strength of reinforced concrete structures .
  • Red Mud had the desired high iron content for the formation of cements of the type disclosed in the Mehta patent; and in accordance with a further aspect of the invention it was determined that the high alkali content of cement kiln dust surprisingly did not adversely affect the properties of the cement, unlike its effect on Portland type cements, as discussed above.
  • Red Mud In addition to the major constituents of (1) Red Mud and (2) CKD, it is desirable to add lesser quantities of additional materials. Since CKD and Red Mud do not have the proper amount of sulfur tri-oxide for a strong high iron type cement, some sulfur containing material such as gypsum should be added. Additional calcium oxide in the form of lime is often needed, depending on the calcium oxide content of the CKD and Red Mud. Depending on the levels of concentration of aluminum oxide in the Red Mud, additional aluminum oxide may also be added.
  • Red Mud and CKD are used in quantities of at least 20% each.
  • Alumina may be added to increase the Al 2 O 3 content of the mixture, but may not be necessary if the alumina content of the Red Mud is high.
  • Lime may be used to provide additional CaO but may not be necessary if the CaO content of the Red Mud is high.
  • Monovalent Alkalis such as Sodium and Potassium Oxide are normally present in CKD and Red Mud such that the combined percentage of these oxides is greater than 0.5% and may be as much as 1% or 2%, but normally not over 5% and certainly not over 10%.
  • the SO 3 may be added in the form of gypsum.
  • Range A of Table IV The percentages set forth in Range A of Table IV are to be preferred; the percentages of Range B are somewhat broader; and the percentages of Range C constitute an even broader range illustrating the principles of the invention.
  • Figure 1 shows some of the grayish, chocolate colored, brownish cement powder formed in accordance with the invention
  • FIG 2 shows some small test blocks of mortar made from the cement of Figure 1;
  • Figures 3 and 4 are perspective and cross-sectional views, respectively, of a lightweight reinforced concrete beam with an enhanced bond between the high iron concrete of the present invention and the reinforcing steel.
  • Figure 1 shows three tapered test cubes of hardened mortar made using cement having the composition set forth in TABLE III. Further, the fine powder shown in Figure 2 is finely ground clinker having the composition set forth in TABLE III.
  • the mortar used in forming the cubes of Figure 1 was made of a ratio of 2.75 parts of sand, and one-half part water by weight, to one part of cement.
  • the results of compressive strength tests on mortar samples, according to ASTM No. C109 testing procedures is as follows :
  • Figure 3 is a perspective view of a double-T section steel reinforced concrete beam
  • Figure 4 is a cross section taken through the beam of Figure 3, showing the longitudinally extending steel prestressing strands, and the transversely extending steel stirrups.
  • the high iron content cement of the present invention will bond more intimately with the steel reinforcing, and this factor, together with the lighter weight and increased strength of the new cement, will make for improved reinforced concrete structures, having either greater strength, or less concrete to provide the same strength.
  • the cubes which had high compressive strength test results were formed in enclosed chambers formed by bolting two machined parts together, and opening the mold after one day.
  • self pre-stressing may have occurred as a result of the expansive components included in the new cement.
  • EXAMPLE I In the formation of the cement discussed above, the following steps were taken: A batch was prepared con taining: 800 g. of CKD, 882 g. of Red Mud, 375 g. of lime, 500 g. of gypsum and 300 g. of alumina, which were mixed by ball milling for 1/2 hour. CKD was used directly, while red mud had to be sieved through a 100 mesh sieve, in order to exclude large agglomerates present among the fine powder.
  • Rectangular bars of the new cement were formed by casting neat cement paste in plexiglass molds .
  • the bar dimensions were 10 x 10 x 100 mm.
  • Seven samples were made from the new cement, and seven samples from Portland cement also were made for compari son , us ing , in each paste, a cement/water ratio of 2/1 (weight) , and a curing period of 24 hours in a saturated moist air environment .
  • X-ray diffraction was used to identify the main crystalline constituents of the powdered clinker; in addition, efforts were made to identify the chief crystalline products after setting (hydration) of the new cement.
  • the X-ray target used was Cu-K with a Ni filter and 10 3 counts per second. The standard deviation of the counting was 1%, and with 2 degrees/minute scanning rate.
  • the hydrated cement was cast in the plastic sample holder of the X-ray machine, and immersed in water for 6 days after 24 hours in moist air.
  • the strength of the new cement mortar was substantially greater than the compressive strength of Portland cement as indicated in Table V, set forth above.
  • Table VIII shows the relative flexure strength of the new cement and Portland cement after one day.
  • the color of the produced cement ranged from light chocolate brown to dark green, depending on the percentage of gypsum and lime which have been added.
  • the major amounts of raw materials used were CKD, (about 35% weight), and Red Mud, (about 25% weight).
  • the new method and the new cement include the following: (1) it provides a solution to a serious waste disposal problem in the cement and aluminum industries, (2) a high strength cement is produced for construction applications, (3) the raw materials for this cement are available for use, without any further grinding or treatment, in the manufacturing process, (4) the firing temperature of cement is lower than the firing temperature of Portland cement by 200-300 degrees C., (5) there is no need for adding any retarder to the clinker because the alkali problem will be solved during the clinkering processes, and the strength of the produced cement does not depend on the hardening of silica-gel.
  • the total cost of manufacturing the new cement by clinkering CKD and red mud is more economically attractive than the cost of manufacturing Portland cement, due to the low cost of the raw materials, and to the energy saving in the preparation and firing processes of the cement clinker.
  • Hydrated Cement Constituents of the hydrated cement after seven days of curing were identified by analysis of the X-ray pattern.
  • the major constituents of the hydrated cement are set forth in the associated Table X. It was observed that the peaks are shifted slightly, some of them are missing, and considerable over-lapping has occurred.
  • a batch of 500 g. was mixed, using 250 g. CKD and 250 g. Red Mud.
  • the mixture was blended in V-blender for one hour, then heated to 1250 C in a fire clay crucible and sintered for one hour.
  • the cooling process was handled by immersing the crucible wall in water, then blowing a stream of cooled air on the unwetted surface of the melt until it was possible to handle the warm crucible with bare hands.
  • the mixture reacted with the crucible; therefore, the crucible had to be broken in order to get the clinker out.
  • the clinker was then crushed in a porcelain mortar and sieved through #325 mesh screen. About 50 g.
  • composition III A batch of 200 g. was prepared using the same procedure as in composition III. But at 1250 C there was partial melting and there was no glass phase in the crucible. At 1350 C. there was a glass phase and the mixture was sintered for one hour at that temperature. Same results as for composition III. The clinker color of composition II was dark green and when mixed with water it turned to brown green. Also, there was no cementitious reaction.
  • Example V Similar to Example V.
  • the sintering temperature was 1300 C.
  • the clinker color was yellow. Set up in one day.
  • compositions for the CKD and Red Mud which were used in the foregoing examples, were given.
  • the compositions given from other sources are also of interest, as showing that the compositions of CKD and Red Mud may differ significantly. More specifically in the following Tables XI and XII, two such alternate compositions are listed.
  • Tables XIV and XV are some analyses of Red Mud (Table XIV) and brown mud (Table XV) which were courteously supplied by ALCOA, P. O. Box 300, Bauxite, Arkansas 72011.
  • the Red Mud is filter cake from the filters used in deliquoring the Red Mud following a leaching process step.
  • the brown mud sample is filter cake from rotary drain vacuum filters used for separating and washing the residue from leaching Red Mud/limestone/soad ash sinter.
  • Example XI set forth below, CKD as set forth in Table I was employed, and two types Of Red Mud were used, that set forth in Table II and also brown mud (referred to in the present case generically as Red Mud) as included in Table XV.
  • Example X the following materials were used: 40% CKD, 25% brown mud, 20% Red Mud, 15% CaSO 4 , 10% Al 2 O 3 .
  • Example XI EXAMPLE XI
  • the following materials were used: 20% CKD, 20% Red Mud, 15% brown mud, 20% CaSO 4 , 15% CaO, 10% Al 2 O 3 .
  • Example X The same treatment was followed as in Example X, and cast mortar cubes appeared to have much the same properties as those of Example X. Compression tests were made on two inch cubes after curing for one day or twenty-four hours in moist air; and the surprising result of compressive strength of about 2490 psi was realized, using ASTM test procedure C109. This figure is in the order of, or somewhat greater than the ultimate compressive strength of Portland cement. Incidentally, the color of the mortar cubes was that of dark chocolate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Treatment Of Sludge (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

On produit un ciment à haute teneur en fer essentiellement à partir de deux sous-produits industriels disponibles en grandes quantités, notamment (1) de la poussière de four à ciment (CKD) et (2) de la boue rouge, sous-produit de l'extraction d'alumine de la bauxite. Des quantités plus petites de chaux (oxyde de calcium) et de gypse (sulfate de calcium), ainsi que de l'oxyde d'aluminium, sont ajoutées, selon les besoins, au CKD et à la boue rouge, et le mélange est chauffé à une température d'environ 1250o et 1400oC, ce qui est bien au-dessous de la température du four dans le cas du ciment Portland. Les granulés obtenus sont pulvérisés pour obtenir un ciment hydraulique léger et robuste ayant une vitesse de prise rapide.
PCT/US1986/000671 1985-04-05 1986-04-03 Utilisation de la poussiere des fours a ciment et des boues rouges pour produire du ciment hydraulique Ceased WO1986005773A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US72016885A 1985-04-05 1985-04-05
US720,168 1985-04-05

Publications (1)

Publication Number Publication Date
WO1986005773A1 true WO1986005773A1 (fr) 1986-10-09

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EP (1) EP0218681A4 (fr)
JP (1) JPS62502399A (fr)
AU (1) AU5669686A (fr)
WO (1) WO1986005773A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2760003A1 (fr) * 1997-02-25 1998-08-28 Council Scient Ind Res Laitier riche en fer, ciment hydraulique et leur procede de preparation
ES2181544A1 (es) * 1999-07-19 2003-02-16 Cemex Central S A De C V Metodo de fabricacion de escoria o clinker de cemento portland utilizando una caldera de lecho fluidizado circulante.
US6767398B2 (en) * 2000-10-30 2004-07-27 James H. Trato Cementitious compositions and cementitious slurries for permanently plugging abandoned wells and processes and methods therefor
KR101101748B1 (ko) 2010-05-07 2012-01-05 한국세라믹기술원 클링커 원료 조성물 및 그 제조방법
CN109485285A (zh) * 2019-01-17 2019-03-19 张江涛 一种用赤泥制备的喷射混凝土用粉体速凝剂及其制备方法
CN115838250A (zh) * 2022-12-01 2023-03-24 济南大学 一种赤泥基掺合料、熟料及其制备方法与应用
CN116553874A (zh) * 2023-05-24 2023-08-08 中建西部建设北方有限公司 一种高性能低碳砂浆及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036657A (en) * 1975-07-23 1977-07-19 Reagents Of The University Of California High iron oxide hydraulic cement
US4249952A (en) * 1980-03-03 1981-02-10 Pennsylvania Engineering Corporation Method for producing cement clinker from cement kiln waste dust
SU897731A1 (ru) * 1979-12-19 1982-01-15 Львовский Ордена Ленина Политехнический Институт Сырьева смесь дл получени железистого цемента
US4432800A (en) * 1982-08-16 1984-02-21 N-Viro Energy Systems Ltd. Beneficiating kiln dusts utilized in pozzolanic reactions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036657A (en) * 1975-07-23 1977-07-19 Reagents Of The University Of California High iron oxide hydraulic cement
SU897731A1 (ru) * 1979-12-19 1982-01-15 Львовский Ордена Ленина Политехнический Институт Сырьева смесь дл получени железистого цемента
US4249952A (en) * 1980-03-03 1981-02-10 Pennsylvania Engineering Corporation Method for producing cement clinker from cement kiln waste dust
US4432800A (en) * 1982-08-16 1984-02-21 N-Viro Energy Systems Ltd. Beneficiating kiln dusts utilized in pozzolanic reactions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0218681A4 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2760003A1 (fr) * 1997-02-25 1998-08-28 Council Scient Ind Res Laitier riche en fer, ciment hydraulique et leur procede de preparation
ES2181544A1 (es) * 1999-07-19 2003-02-16 Cemex Central S A De C V Metodo de fabricacion de escoria o clinker de cemento portland utilizando una caldera de lecho fluidizado circulante.
US6767398B2 (en) * 2000-10-30 2004-07-27 James H. Trato Cementitious compositions and cementitious slurries for permanently plugging abandoned wells and processes and methods therefor
KR101101748B1 (ko) 2010-05-07 2012-01-05 한국세라믹기술원 클링커 원료 조성물 및 그 제조방법
CN109485285A (zh) * 2019-01-17 2019-03-19 张江涛 一种用赤泥制备的喷射混凝土用粉体速凝剂及其制备方法
CN115838250A (zh) * 2022-12-01 2023-03-24 济南大学 一种赤泥基掺合料、熟料及其制备方法与应用
CN115838250B (zh) * 2022-12-01 2023-10-27 济南大学 一种赤泥基掺合料、熟料及其制备方法与应用
CN116553874A (zh) * 2023-05-24 2023-08-08 中建西部建设北方有限公司 一种高性能低碳砂浆及其制备方法

Also Published As

Publication number Publication date
JPS62502399A (ja) 1987-09-17
AU5669686A (en) 1986-10-23
EP0218681A4 (fr) 1987-07-29
EP0218681A1 (fr) 1987-04-22

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