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United States Patent (19) (11) Patent Number: 4,838,941 Hill 45 Date of Patent: Jun

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United States Patent (19) (11) Patent Number: 4,838,941 Hill 45 Date of Patent: Jun United States Patent (19) (11) Patent Number: 4,838,941 Hill 45 Date of Patent: Jun. 13, 1989 (54) MAGNESIUM CEMENT (56) References Cited U.S. PATENT DOCUMENTS 75) Inventor: Robert G. D. Hill, Hendon, Australia 2,526,837 10/1950 Woodward ......................... 106/106 2,703,273 3/1955 Robertson et al. ................. 106/106 73) Assignee: Ausmintec Corp. Limited, Hendon, Australia FOREIGN PATENT DOCUMENTS 520027 i2/1955 Canada ................................ 106/106 34.8503 9/1972 U.S.S.R. .............................. 423/472 (21) Appl. No.: 599 17208 7/1895 United Kingdom ................ 106/106 Primary Examiner-Mark L. Bell (22 Filed: Jan. 6, 1987 Attorney, Agent, or Firm-Klauber & Jackson (30) Foreign Application Priority Data 57 ABSTRACT A reaction product of at least one of magnesium carbon Jan. 7, 1986 AU) Australia .............................. PH4143 ate and magnesium silicate, with a metal chloride at a temperature exceeding 300 C. Such a product, when 51) Int. Cl." ........................... C04B 9/02; C04B 9/04 mixed with water, sets to be an immensely strong mag 52 U.S. Cl. .................................... 106/106; 106/105; nesium cement. It may have aggregates of various types 423/163; 423/178; 42.3/472; 423/473 mixed with it. 58 Field of Search ................ 106/105, 106; 423/163, 423/178, 472, 473 18 Claims, 2 Drawing Sheets WASTE CACUM CHORIDE BRINES GYPSUM & ANHYDRTE SODIUM CHORDE MURIATE OF POTASH MLK OF MAGNESIA CAUSTIC MAGNESA REFRACTORY MAGNESA ASUM MAGNESUM CEMENT B ABSORBTION CEMENT TOWER8 E WASTE INDUSTRIAL CARBONATES ACDS U.S. Patent Jun. 13, 1989 Sheet 1 of 2 4,838,941 WASTE CALCIUM CHORIDE BRINES 1 2 GYPSUM & ANHYDRTE SODUM CHLORIDE CARBONATES MURATE 6 OF POTASH MLK OF 7 MAGNESA CAUSTC HL II MAGNESA 16 REFRACTORY MAGNESA |HCL GAS (\ TOWER WER liftion8 14 HYDROCHLORIC ACD CARBO N DOXDED WASTE ACDSNiA CARBONATES F G. 4,838,941 1 2 will, however, react at ambient temperature with mod MAGNESIUM. CEMENT erately concentrated solutions of magnesium chloride to produce Sorel cement. Sorel cement made in this This invention relates primarily to a product which, manner is frequently erroneously referred to as magne by addition of water, sets to a magnesium cement hav sium oxychloride cement. Magnesium sulphate has been ing superior strength characteristics. In some embodi substituted for magnesium chloride to produce cements ments of the invention, the invention is directed to a of lesser mechanical strength and severe shrinkage method of production of magnesium cement, and also to characteristics which have been erroneously referred to the means of production. - as magnesium oxysulphate cements. 10 The term magnesium oxychloride implies a formula BACKGROUND OF THE INVENTION Mg-O-Cl. Since these products produce hydrogen The cement in most common use is Portland cement, chloride on heating in a dry atmosphere, this formula is which is made by finely grinding limestone and clay or obviously incorrect. Consequently some writers have shale and calcining with some added gypsum, to tem given the so-called magnesium oxychloride components peratures approaching or in excess of 1600 degrees 15 the formula MgO-HCl. centigrade. The mixture after calcining is known as This formula is completely at variance with chemical clinker and requires further fine grinding, and fre analysis of "sorel' cements, which have been given quently the addition of gypsum, to produce Portland formulae as below by various authorities. cement. In some locations volcanic rocks can be substi All reliable analyses of these "oxychloride' cements tuted for the clay and shale. 20 agree on some or all of the following empirical formulas Portland cement when mixed with water and aggre being acceptable. gates sets to a concrete which, according to ASTM (Australian Standard) requirements, should achieve a compressive strength of 3000 psi or 20 mPa after 28 Ratio Mg Ratio days. To achieve maximum mechanical strength, the 25 Formula Mg:Cl Content Mg:OH amount of water used in the mixing must be kept to a 2 Mg(OH)2 MgCl24H2O 1.0 Mg = 25% 0.52 minimum, and the casting of concrete made with 3 Mg(OH)2 MgCl28 H2O 1.35 Mg = 23% 0.40 Portland cement is consequently difficult if high me 5 Mg(OH)2 MgCl28 H2O 2.0 Mg = 27% 0.47 chanical strength is required. Surface treatment of cast 9 Mg(OH)2 MgCl2.5H2O 3.38 Mg = 34% 0.61 concrete is also usually necessary to improve appear 30 CC. All these products result from an interaction of reactive Portland cement is presently produced in very large magnesium oxide with magnesium chloride in aqueous quantities, but, because of the need to finely grind the solution, at temperatures between 0° C. and 100 C. materials both before and after calcining, and because of Numerous other authorities still accept the 2,3,5 or 9 the cost of achieving the high calcining temperatures, 35 compounds as separate compounds with H2O content and the cost component for energy requirements, the varying significantly with the conditions of formation. cost is very high (by comparison with this invention). All sorel or magnesium oxychloride cements referred For example, in South Australia, the energy cost is to in the literature comply approximately with the for about six times the cost of the basic materials. mulae given above and all decompose on heating to An object of the invention is to provide a cement 40 about 600 degrees C., evolving hydrochloric acid and which can be produced without the need to finely grind leaving a residue of magnesium oxide. They are not the natural limestone and shale raw materials, or the resistant to continuous immersion in water, and, having calcined clinker, and without the need to attain high a pH of between 4.8 and 5.2, are corrosive to steel. calcining temperatures, and yet be able to make use of Another commonly used cement is formed by calcin readily available and inexpensive basic materials. 45 ing limestone minerals with high magnesium content, Various types of magnesium cement are already also at very high temperature, along with clays and known, the most relevant to this invention being Sorel shales, to produce a product similar to Portland cement. cement. In the production of Sorel cement, high grade magnesite or magnesium carbonate is calcined to form OTHER PRIOR ART reactive magnesium oxide (MgO). If the calcining tem 50 In addition to the Portland and magnesium cements perature is raised to 1500 C. or higher, a non reactive referred to above, reference can be made to the follow product called deadburned magnesia is obtained. This ing patent literature: product finds application in blast furnaces and in refrac U.S. Pat. No. 4,003,752, Isohata et al, utilising active tory applications. It lacks mechanical strength, how magnesia (MgO), magnesium sulphate (MgSO4) and ever, and is not used where significant mechanical 55 pulp. One object of this invention therein is to reduce strength is required. It is not used in Sorel cement. the sulphur content as much as possible, since, in the If on the other hand temperatures of calcining are cement of this invention, it will increase shrinkage and reduced to not less than 750 C., (and quite commonly reduce desirable strength characteristics. 900' C.) reactive or caustic magnesia is produced. This P.C.T. WO85/04860, Delphic Research, relates to a material has a useful mechanical strength, although paint-like slurry which uses an "oxychloride' cement when maintained in a moist condition for long periods with high alumina mono calcium aluminate cement and of time, it very slowly converts to basic magnesium colloidal silica. That invention seeks to reduce to a carbonate. This reaction is much slower than the corre minimum the oxychloride (Sorel) cement content be sponding reaction involving quick lime or hydrated cause it reduces desirable strength characteristics. The lime, and many years are required to achieve a stable 65 other constituents are not used in any admixture. mechanical strength. U.S. Pat. No. 3,778,304, Thompson. Relates to an Caustic magnesium oxide produced by calcining oxychloride cement containing a frothing agent and, (as magnesite attemperatures between 750° C. and 1500 C. said), is avoided in the invention herein. 4,838,941 3 4. U.S. Pat. No. 4,419,196, Beckerick. Relates to abrupt (a) react other of that hydrogen chloride with magne hardening of oxychloride cement. sium carbonate or silicate to form further MgCl2 U.S. Pat. No. 4,339,278, Duyster. Relates to Sorel (b) form chlor-oxy-hydroxy compounds of magne (oxychloride) cement. sium (MgO.Mg(OH)2.MgCl22) where x, y and Z are U.S. Pat. No. 4,352,694, Smith-Johannsen. Relates to 5 integers ranging between 1 and 12, before further reac oxychloride cement. tion at a temperature exceeding 300° C. P.C.T. WO85/00586, Shubow. Relates to mixture of In some instances, the entire output of the reaction is magnesium oxide, silicate, aggregate and mono-alumini useful as magnesium cement, without the need to sepa um-phosphate acidic solution. Although phosphates can rately form the MgO, MgO-MCl) and (Mg.O.M- be tolerated, they are not necessary in the invention 10 g(OH)2.MgCL2) from the other reaction products, or herein. chemicals which are present but are not reaction prod The above references constitute the closest art known lictS. to the Applicant, but all relate to Sorel cement (in one In other instances, where the raw material input in form or another). cludes larger alkali metal carbonate components, and No prior art at all is known to the Applicant relating 15 smaller chloride components, a very valuable magne to a reaction product of magnesium containing mineral sium cement can be produced with a smaller amount of and a metal chloride at a temperature of between 300 chloroxy-magnesium compound, for example a cement C.
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