US3443976A - Mineral grinding aids - Google Patents

Mineral grinding aids Download PDF

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Publication number
US3443976A
US3443976A US496144A US3443976DA US3443976A US 3443976 A US3443976 A US 3443976A US 496144 A US496144 A US 496144A US 3443976D A US3443976D A US 3443976DA US 3443976 A US3443976 A US 3443976A
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United States
Prior art keywords
additive
grinding
mineral
pack set
minerals
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Expired - Lifetime
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US496144A
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English (en)
Inventor
Vance H Dodson
Frank G Serafin
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WR Grace and Co
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WR Grace and Co
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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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • C04B24/128—Heterocyclic nitrogen compounds
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/52—Grinding aids; Additives added during grinding

Definitions

  • This invention relates to grinding minerals, and more particularly to the use of an additive for improving the efficiency in grinding minerals and improving the pack set characteristics of minerals.
  • a grinding operation is generally necessary in order to reduce the particular mineral to a relatively small particle size. It is desirable in this grinding step to have as efficient an operation as possible, that is, to reduce the mineral to the desired particle size at a relatively rapid rate.
  • a grinding aid is employed to promote an increase in efiiciency, either by increasing the rate of production or by increasing the fineness of the particles at the same rate of production without having adverse effects on any of the properties of the ground product.
  • pack set as used herein is intended to refer to the agglomeration or adhesion of particles by, e.g., storing or transporting in bulk. Adhesion results from sur face forces, the majority of which are created during the grinding 0f the minerals.
  • Pack set index is a relative term which numerically indicates how prone a particular material is to start flowing after it is stored or transported in bulk.
  • Pack set index ratio is the relative pack set index of the untreated sample compared to the treated sample. This ratio is used to permit comparison between different samples of the mineral.
  • Pack set index is determined in the following manner: 100 grams of the mineral is placed in a 250 milliliter Erhlenmeyer flask set on top of a variable vibrator. The flask containing a mineral is vibrated seconds after which time it is removed from the vibrator and fed into a jig with the axis of the flask lying horizontally. The flask is then rotated about its axis until the mineral which is compacted on the bottom of the flask collapses. The flask is twisted by turning at 180 angles at approximately 100 twists per minute. The number of 180 twists required for the mineral sample to collapse establishes the pack set "ice index. Thus, the greater the energy requirement to break up the bed, the higher will be the pack set index.
  • R is an alkaryl or aryl radical;
  • R is hydrogen or an alkyl radical;
  • R is hydrogen, hydroxyl, alkyl or aryl radical;
  • R is hydrogen, alkyl, alkoxy or alkylhydroxy radical;
  • n is an integer from 0 to 5, inclusive.
  • R is preferably alkylphenyl or phenyl radical. It should also be understood that the aryl radical may contain substituents such as halogen, e.g., chlorine and bromine, alkyl, amino or hydroxyl radicals.
  • the alkyl groups represented by R, R R and R are preferably lower alkyl, i.e., l to 6 carbon atom alkyl radicals.
  • pyrrolyl, pyrrolidyl, morpholino, morpholinyl and piperadyl, as used therein are intended to include the substituted radicals which are known to the art, e.g., N-methylmorpholino, and 4-(2-aminoethoxy) ethylmorpholine.
  • the additives of Formulae B and C are particularly preferred because of the particularly advantageous pack set properties as well as the increased grinding efliciency achieved with these classes of materials.
  • the additive is interground with the mineral in the grinding mill to provide increased grinding efficiency as well as other advantageous results, e.g., inhibiting pack set of bulk stored materials or inhibiting the formation of foam in some mineral processing applications. It has also been found that the novel additive of the present inven tion also serves to provide fluidity to the ground minerals when they are being transported by conveying systems, particularly by pneumatic air systems.
  • mineral as used herein is intended to refer to naturally occurring inorganic minerals, such as phosphate rock, partially processed minerals such as concentrated iron ore, and mixtures of minerals such as cement clinker or ceramics.
  • Such minerals which can be processed with the additive of the present invention, mention may be made of beryllium oxide, limestone, gypsum, clays, and bauxite.
  • the additive of the present invention is particularly preferred for use with cement, and cement-forming materials particularly portland cement.
  • Portland cement represents a class of hydraulic cements and is comprised essentially of two calcium silicates and a lesser amount of calcium aluminate. These cements are In a particularly preferred embodiment the additive employed is morpholine and morpholinyl derivatives. Various grades and purities of the morpholine compounds are employed with satisfactory results.
  • a particularly preferred source of morpohline type compounds is a byproduct produced by heating an intimate mixture of finely divided 5 from the continuous commercial production of heterocalcareous material (limestone) and argillaceous material cyclic amines. The by-product contains a mixture of (clay) to fusion to form a clinker. The clinker is ground aliphatic and heterocyclic monoand diamines.
  • Table 3 shows a typical analysis of a by-product which qualities in the finished cement. It is to the clinker that is predominantly a mixture of 4-'(2-aminoethoxy) ethylthe novel additive of this invention is preferably added to morpholine, 2(4-morpholylethoxy) ethanol and bis-2-(4- increase grinding efiiciency and to inhibit subsequent pack morpholinyl) ethyl ether. set in the finished cement. Table The additives of the present invention are employed in either dry or liquid form.
  • the additive Tit atable amine Meq./g 7.52 is in liquid form to permit accurate metering into the Primary amine Meq./g 1.66 mineral stream.
  • the additive can be utilized by emulsifying it Total nitrogen Meq./g 7.93 with a suitable wetting agent, e.g., sodium dodecyl ben- Total acetylatable material Meq./g 7.02 zene sulfonate.
  • a suitable wetting agent e.g., sodium dodecyl ben- Total acetylatable material Meq./g 7.02 zene sulfonate.
  • the addition is accomplished either prior Specific gravity 20/20 C-.. 1.078 to the grinding or the additive is introduced into the grind- Water content wt. percent-.. 0.08 ing mill simultaneously with the mineral.
  • the additive of the present invention is employed as the sole grinding aid or with a mixture of one or more TABLE 4 grinding aids or with additives known to the art other Amountotadditive (percent Blaine surface than grinding aids, e.g., set retarders or accelerators, in mud smd) Pack Set index the case of cement. Bgmk a, 441 12. 0 The additive is employed effectively over a relatively 5 36o5 L0 wide range.
  • the preferred range is about 0.001 to 1%, r m the a ve table it can be seen that the use of d more f bl bo t 0,005 to abo t 01% b sed on even a very small amount of additive results in an increase the weight of the mineral, i.e., weight of additive solids in grinding efficiency of about 164 units as Well s a based on weight of mineral solids (herein referred to as stantial decrease in pack set index. solids on solids).
  • the novel additive described in Table 3 was also used about 0.05% of the additive based on the weight of the to grind phosphate rock. After grinding phosphate rock mineral is employed.
  • the 3,441 acetylated amine acetate is produced by the addition of 3-8; Egg acid anhydride to the amine instead of the acid. 31480
  • the following table illustrates the use of the reaction 38% 2% product of the amine described in Table 3 and acetic acid 3:542 (pH 8) in grinding cement clinker.
  • the Type 1 cement 3-8? 238 clinker and gypsum were ground for 4095 revolutions in 01 550 a laboratory mill heated to 200 F.
  • pack set data is reported on cement inter- Air ground with the additives of this inventioniiii iii iiii i giid) i iliiifi ifi Pack set index ns i ii biiis TABLE 2 Blank 3,590 0 10.0 0.058 3,850 0 10.3 Additiofisgle Additive (Ween solid) Pack set; index From Table 5 it can be seen that the grinding efficiency Blank 12 6 and pack set properties are increased and no air is en- Anilinez 0. 05 10: 0 trained. gif 8-8; As stated above, the present invention is also directed N-metliyl morpholine 0: 01 11:3 7 to mixtures of additives.
  • a particularly preferred mixture P'wgindme 3-8; 5% is prepared from the amine described in Table 3, tri- 0101 s10 ethanolamine and acetic acid.
  • a preferred source of tri- 3:8? g g ethanolamine is the residue product obtained in produc- Diphenylamine- 0.05 7.3 tion of ethanolamines.
  • the exact composition of the residue product varies within certain limits and, therefore the residue product may contain one or more of mono-, or diethanolamine in addition to the triethanolamine.
  • One such residue product has the following analysi before neutralization TABLE 6 Triethanolamine percent by volume 45 to 55 Equivalent weight 129 to 139 Tertiary amine meq./gm 6.2 to 7.0 Water by weight, max 0.5 Density lbs./gal 9.49
  • the following table illustrates the grinding efficiencies obtained using the reaction product of acetic acid and a 5050 (by weight) mix of the amines of Table 3 and Table 6.
  • the pH of the mixture was 8.
  • Type I cement clinker and gypsum were ground in' a laboratory mill at 220 F.
  • Pack set index therewith the said additive being compounds selected from the group consisting of morpholine, N-methylmorpholine, and a byproduct from the continuous commercial production of heterocyclic amines consisting predominantly of 4-(2-amin'oethoxy) ethylmorpholine, 2-(4-morpholethoxy) ethanol, and bis-2-(4-morpholinyl) ethyl ether.
  • a composition comprising a mineral and intimately admixed therewith, from 0.001 to 1% based on the weight of the mineral of a mixture of (1) an aliphatic organic acid having 2-20 carbon atoms, (2) a residue product of ethanolamine synthesis, and (3) a compound selected from the group consisting of morpholine, N-methylmorpholine, and a byproduct from the continuous commercial production of heterocyclic amines consisting predominantly of 4-(2-aminoethoxy) ethylmorpholine, 2-(4- morpholylethoxy) ethanol, and bis-2-(4-rnorpholinyl) ethyl ether, said residue product being predominantly triethanolarnine and having the following properties before neutralization:
  • Triethanola-mine 45 to by volume Equivalent weight 123 to 139 Tertiary amine 6.2 to 7.0 meq./ gm. Water 0.5% by weight, max. Density 9.49lbs./ga1.
  • composition of claim 1 wherein the mineral is portland cement.

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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)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Dental Preparations (AREA)
US496144A 1965-10-14 1965-10-14 Mineral grinding aids Expired - Lifetime US3443976A (en)

Applications Claiming Priority (1)

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US49614465A 1965-10-14 1965-10-14

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US (1) US3443976A (OSRAM)
DE (1) DE1542190A1 (OSRAM)
ES (1) ES332200A1 (OSRAM)
FR (1) FR1556955A (OSRAM)
GB (1) GB1151604A (OSRAM)
SE (1) SE335697B (OSRAM)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619221A (en) * 1970-03-25 1971-11-09 Grace W R & Co Amine formate accelerator additives for portland cement compositions
US3950182A (en) * 1973-11-20 1976-04-13 Imperial Chemical Industries Limited Treatment process
DE3245843A1 (de) * 1982-12-10 1984-06-14 Teroson Gmbh, 6900 Heidelberg Mahlhilfsmittel und diese enthaltende mineralmischung
US4645130A (en) * 1984-12-04 1987-02-24 American Cyanamid Company Method for treating carbide-based desulfurizing reagents for injection into molten iron
US5131600A (en) * 1989-02-13 1992-07-21 The Dow Chemical Company Alkanol amine grinding aids
US5244155A (en) * 1991-06-24 1993-09-14 The Dow Chemical Company Solid-solid separations utilizing alkanol amines
US6149725A (en) * 1998-03-09 2000-11-21 Sika Ag, Vorm. Kaspar Winkler & Co. Injection cement comprising corrosion inhibitors
EP2660217A1 (de) * 2012-05-03 2013-11-06 Construction Research & Technology GmbH Mahlhilfsmittel für mineralische Bindemittel
US20160176758A1 (en) * 2013-07-12 2016-06-23 Sika Technology Ag Adjuvant combination of a milling assistant and a concrete admixture for accelerated hydration of cementitious binders

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8201457A (nl) * 1981-06-02 1983-01-03 Grace W R & Co Hydraulisch cement, werkwijze voor de bereiding daarvan, en daarbij te gebruiken hulpstoffen.
DE19617357A1 (de) * 1996-04-30 1997-11-06 Heinrich Otto Paul Dr Kaspar Zementzusatz

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2857286A (en) * 1955-11-23 1958-10-21 Missouri Portland Cement Compa Manufacture of portland cement
US3042718A (en) * 1958-12-17 1962-07-03 Ici Ltd Urea compositions
US3088837A (en) * 1959-09-23 1963-05-07 Gen Aniline & Film Corp Preparation of paint compositions containing a pyrrolidone compound
US3278269A (en) * 1963-08-13 1966-10-11 Freeport Sulphur Co Sulphur treatment
US3305491A (en) * 1963-05-23 1967-02-21 Prod Chim D Auby Soc D Anti-caking agent
US3325105A (en) * 1964-07-17 1967-06-13 Grace W R & Co Mineral grinding aids and process of grinding
US3329517A (en) * 1965-02-05 1967-07-04 Grace W R & Co Cement additives composed of ethanolamine salts

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2857286A (en) * 1955-11-23 1958-10-21 Missouri Portland Cement Compa Manufacture of portland cement
US3042718A (en) * 1958-12-17 1962-07-03 Ici Ltd Urea compositions
US3088837A (en) * 1959-09-23 1963-05-07 Gen Aniline & Film Corp Preparation of paint compositions containing a pyrrolidone compound
US3305491A (en) * 1963-05-23 1967-02-21 Prod Chim D Auby Soc D Anti-caking agent
US3278269A (en) * 1963-08-13 1966-10-11 Freeport Sulphur Co Sulphur treatment
US3325105A (en) * 1964-07-17 1967-06-13 Grace W R & Co Mineral grinding aids and process of grinding
US3329517A (en) * 1965-02-05 1967-07-04 Grace W R & Co Cement additives composed of ethanolamine salts

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619221A (en) * 1970-03-25 1971-11-09 Grace W R & Co Amine formate accelerator additives for portland cement compositions
US3950182A (en) * 1973-11-20 1976-04-13 Imperial Chemical Industries Limited Treatment process
DE3245843A1 (de) * 1982-12-10 1984-06-14 Teroson Gmbh, 6900 Heidelberg Mahlhilfsmittel und diese enthaltende mineralmischung
US4491480A (en) * 1982-12-10 1985-01-01 Teroson G.M.B.H. Grinding aid and mineral mixture containing it
US4645130A (en) * 1984-12-04 1987-02-24 American Cyanamid Company Method for treating carbide-based desulfurizing reagents for injection into molten iron
US5131600A (en) * 1989-02-13 1992-07-21 The Dow Chemical Company Alkanol amine grinding aids
US5244155A (en) * 1991-06-24 1993-09-14 The Dow Chemical Company Solid-solid separations utilizing alkanol amines
US6149725A (en) * 1998-03-09 2000-11-21 Sika Ag, Vorm. Kaspar Winkler & Co. Injection cement comprising corrosion inhibitors
EP2660217A1 (de) * 2012-05-03 2013-11-06 Construction Research & Technology GmbH Mahlhilfsmittel für mineralische Bindemittel
WO2013164212A1 (en) * 2012-05-03 2013-11-07 Construction Research & Technology Gmbh Grinding additive for mineral binders
CN104271529A (zh) * 2012-05-03 2015-01-07 建筑研究和技术有限公司 用于无机粘合剂的研磨添加剂
US9181128B2 (en) 2012-05-03 2015-11-10 Construction Research & Technology Gmbh Grinding additive for mineral binders
CN104271529B (zh) * 2012-05-03 2016-05-11 建筑研究和技术有限公司 用于无机粘合剂的研磨添加剂
RU2622563C2 (ru) * 2012-05-03 2017-06-16 Констракшн Рисёрч Энд Текнолоджи Гмбх Добавка размола для минеральных вяжущих
US20160176758A1 (en) * 2013-07-12 2016-06-23 Sika Technology Ag Adjuvant combination of a milling assistant and a concrete admixture for accelerated hydration of cementitious binders
US10752546B2 (en) * 2013-07-12 2020-08-25 Sika Technology Ag Adjuvant combination of a milling assistant and a concrete admixture for accelerated hydration of cementitious binders

Also Published As

Publication number Publication date
GB1151604A (en) 1969-05-14
ES332200A1 (es) 1967-07-16
SE335697B (OSRAM) 1971-06-01
DE1542190A1 (de) 1970-03-26
FR1556955A (OSRAM) 1969-02-14

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