PARTIALLY PROTONATED ALKANOLAMINE COMPOSITION, AND USE IN A MILL

Abstract

The invention relates to a composition (C) comprising from 10 to 99 wt. % secondary or tertiary alkanolamine (A) in the form of a salt, preferably an inorganic acid salt, and from 1 to 90 wt. % of non-salified alkanolamine (A).

Claims

1. A composition (C) comprising from 10 to 99 weight % secondary or tertiary alkanolamine (A) in the form of a salt, and from 1 to 90 weight % of non-salified alkanolamine (A).

2. The composition (C) according to claim 1 comprising from 50 to 99 weight % of secondary or tertiary alkanolamine (A) in the form of a salt, and from 1 to 50 weight % of non-salified alkanolamine (A).

3. The composition according to claim 1, wherein the alkanolamine salt is a halide acid salt, or a salt of sulfuric acid, phosphoric acid, phosphonic acid, or a hydrogensulfate, carbonate or hydrogencarbonate salt.

4. The composition according to claim 1, wherein the alkanolamine salt is a halide acid salt or sulfuric acid salt.

5. The composition according to claim 1, wherein the alkanolamine salt is a hydrochloric acid salt.

6. The composition according to claim 1, wherein the alkanolamine is an alkanolamine of formula (I) N(R.sup.1OH)(R.sup.2)(R.sup.3) (I) wherein the R.sup.1, the same or different, are a linear or branched alkyl group having 1 to 10 carbon atoms, R.sup.2 is H or R.sup.1—OH group, R.sup.3 is H, a linear or branched alkyl group having 1 to 10 carbon atoms, a R.sup.4—OH group where R.sup.4 is a linear or branched alkyl group having 1 to 10 carbon atoms, or an (alkyl)-N(alkyl-OH).sub.2 group, the alkyl being linear or branched and having 1 to 5 carbon atoms, at least one of R.sup.2 and R.sup.3 differing from H.

7. The composition according to claim 1, wherein the alkanolamine is selected from the group consisting of among triisopropanolamine (TIPA), diisopropanol amine (DIPA), di ethanol-isopropanolamine (DEIPA), ethanol-diisopropanolamine (EDIPA), N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (THEED) and methyldiethanolamine (MDEA).

8. The composition according to claim 1, wherein the alkanolamine is selected from the group consisting of triisopropanolamine (TIPA), diethanol-isopropanolamine (DEIPA) and ethanol-diisopropanolamine (EDIPA).

9. The composition according to claim 1, wherein the alkanolamine is triisopropanolamine (TIPA).

10. A method of using a secondary or tertiary alkanolamine for grinding at least one hydraulic binder comprising: converting the alkanolamine (A) to a partially salified form, to obtain a composition (C) according to claim 1; adding composition (C) to a mill.

11. (canceled)

12. The method according to claim 10, wherein alkanolamines other than the secondary or tertiary alkanolamine (A) of composition (C), salts of the secondary or tertiary alkanolamine (A) of composition (C), glycols, glycerols, water-reducing additives and high-range water reducers; surfactants, carboxylic acids, and/or setting retardants are used in addition to the alkanolamine salt.

13. The method according to claim 10 wherein one or more defoamers are used in combination with the alkanolamine salt.

14. A composition comprising: at least one hydraulic binder; a composition (C) according to claim 1; and optionally water and aggregates.

15. The composition according to claim 14, further comprising one or more defoamer compounds.

16. The composition according to claim 1, wherein the alkanolamine salt is an inorganic acid salt.

17. The composition according to claim 7, wherein R.sup.4 is (CH.sub.2—CH.sub.2)—N(CH.sub.2—CH.sub.2—OH).sub.2.

18. The method according to claim 12, wherein converting the alkanolamine (A) to a partially salified form is by means of an inorganic acid.

19. The method according to claim 14, wherein: the salts are selected from the group consisting of sodium chloride, calcium chloride, sodium thiocyanate, calcium thiocyanate, sodium nitrate and calcium nitrate and mixtures thereof, the water-reducing additives and high-range water reducers are selected from the group consisting of sulfonated salts of naphthalene and formaldehyde polycondensates, commonly called polynaphthalene sulfonates or naphthalene-based superplasticizers; sulfonated salts of melamine and formaldehyde polycondensates, commonly called melamine-based superplasticizers; lignosulfonates; sodium gluconate and sodium glucoheptonate; polyacrylates; polyarylethers (PAE); polycarboxylic acid-based products; and products based on polyalkoxylated polyphosphonates, the carboxylic acids are selected from the group consisting of acetic, adipic, gluconic, formic, oxalic, citric, maleic, lactic, tartaric, and malonic acids, and/or the setting retardants are chosen from sugar-, molasses- or vinasse-based, and mixtures thereof.

20. The method according to claim 15, wherein the polycarboxylic acid-based products are polycarboxylate comb-copolymers, which are branched polymers having a main chain carrying carboxylic groups and side chains composed of polyether-type sequences.

21. The method according to claim 16, wherein the polycarboxylate comb-copolymers are poly [(meth)acrylic acid—grafted—ethylene polyoxide.

Description

EXAMPLE 1

[0078] In this example, a mixture is used of triisopropanolamine (TIPA) and a hydrochloric acid salt of triisopropanolamine. It is obtained by mixing triisopropanolamine with different concentrations of hydrochloric acid to obtain TIPA:HCl molar ratios of 1:0.70 and 1:0.85. The molar ratio of amine and acid is therefore non-stoichiometric with excess amine relative to acid, leading to partial protonation of the amine.

[0079] To obtain a mixture with a TIPA:HCl molar ratio of 1:0.70, an amount of 156.3 g of triisopropanolamine at a weight concentration of 64% in water is mixed with 36.1 g of 37 weight % hydrochloric acid. Via acid-base reaction between the amine and the acid, 70 weight % of TIPA is converted to hydrochloric acid salt of triisopropanolamine, while 30 weight % of TIPA remains in non-protonated form. Similarly, to obtain a TIPA:HCl molar ratio of 1:0.85, an amount of 156.3 g of triisopropanolamine at a weight concentration of 64% in water is mixed with 43.79 g of 37 weight % hydrochloric acid. Via acid-base reaction between the amine and acid, 85% weight % of TIPA is converted to hydrochloric acid salt of triisopropanolamine, while 15 weight % TIPA remains in non-protonated form.

[0080] The two mixtures obtained are in the form of a clear solution. Via back acid-base titration, it is possible to determine the amount of protonated amine (TIPA+HCl) in each mixture. If sodium hydroxide (0.1 mol/L) is added to the mixture of TIPA+HCl and TIPA, a jump in pH is recorded at the equivalence point volume of sodium hydroxide, characteristic of the acidity constant of the chemical compound (TIPA/TIPA+HCl). The volume of sodium hydroxide added up to the equivalence point therefore allows determination of the concentration of the hydrochloric acid salt of triisopropanolamine in the solution.

EXAMPLE 2

[0081] With the same type of chemical reaction, it is possible to prepare a mixture of diethanol-isopropanolamine and hydrochloric acid salt of diethanol-isopropanolamine (DEIPA) at different molar ratios. To obtain a mixture with a DEIPA:HCl molar ratio of 1:0.70, an amount of 117.6 g of diethanol-isopropanolamine at a weight concentration of 85% in water is mixed with 51.8 g of 37 weight % hydrochloric acid. To obtain a mixture with a DEIPA:HCl molar ratio of 1:0.85, an amount of 117.6 g of diethanol-isopropanolamine at a weight concentration of 85% in water, is mixed with 62.9 g of 37 weight % hydrochloric acid. After acid-base reaction, these formulas respectively contain 70 and 85 weight % of diethanol-isopropanolamine in protonated form (DEIPA+HCl). The content of diethanol-isopropanolamine hydrochloric acid salt (DEIPA+HCl) in these mixtures can be confirmed by back acid-base titration with sodium hydroxide.

EXAMPLE 3

[0082] With the same type of chemical reaction, it is possible to prepare a mixture of triisopropanolamine (TIPA) and sulfuric acid salt of triisopropanolamine with a protonation rate of triisopropanolamine lower than 100 weight %. To obtain a solution containing 70 weight % of protonated triisopropanolamine, 117.6 g of triisopropanolamine at a weight concentration of 64% in water are mixed with 18.9 g of 95 weight % sulfuric acid. The formula obtained then contains a mixture of TIPA+H.sub.2SO.sub.4 and TIPA. The protonated amine content of this mixture can again be confirmed by back acid-base titration with sodium hydroxide.

EXAMPLE 4

[0083] On CEM II/A-V 42.5 N cement containing 15 weight % fly ash with target Blaine specific surface area of 4000 cm.sup.2/g, a dosage of 90 ppm TIPA allows an 11% increase in cement mill capacity. On the other hand, a dosage of 120 ppm TIPA creates harmful effects by causing excessive flowability of the cement powder which becomes highly volatile. The partially protonated TIPA (TIPA:HCl=1:0.85) in TIPA+HCl form does not have any negative impact on cement grinding (no excessive flowability). It even allows a slight increase in mill capacity and leads to enhanced compressive strengths.

TABLE-US-00001 TABLE 1 Dosage Mill capacity 2-day CS 28-day CS Description (ppm) (tph) (MPa) (MPa) Reference  0 70 24.0 55.2 TIPA 90 78 24.5 61.3 TIPA 120 ppm  NA* — — TIPA + HCl 139 ppm** 80 25.2 63.0 (TIPA:HCl = 1:0.85) *Mill emptying **Equivalent to 120 ppm TIPA + 19 ppm HCl.

[0084] This example evidences the fact that in the mill a TIPA content that is too high will impact the efficacy of grinding and leads to a drop in mechanical performance; the placing of TIPA in partial salt form allows these disadvantages to be overcome.

EXAMPLE 5

[0085] In a «half-scale» vertical 2-roller mill, 200 kilograms per hour of CEM I type cement were produced to obtain a cement of target fineness having a Blaine specific surface area of 4000 cm.sup.2/g. In the presence of an activator comprising TIPA with different protonation rates, mill performance was monitored (rate of production in kilograms per hour). At a TIPA dosage of 400 ppm, harmful effects of cement excessive flowability can occur since the powder becomes too volatile, which can be monitored by measuring the pressure between the mill filter inlet and outlet.

[0086] The addition of 400 ppm non-protonated TIPA to the cement allows mill capacity to be increased in relation to the reference without additive, while maintaining Blaine specific surface area of the cement at the target of 4000 cm.sup.2/g. The amine therefore facilitates grinding of the cement and allows an increase in mill performance. Nonetheless, a significant increase in pressure at the filter is recorded compared with the reference without additive. This non-protonated amine promotes dust emissions and the placing in suspension of powder in the mill, which impacts the grinding process. The use of a partially (at 50 weight %) or fully (100 weight %) protonated amine in the form of a hydrochloric acid salt (TIPA+HCl) allows this differential pressure to be reduced. Therefore, the more the rate of protonation of the amine is increased the lesser the dust emissions in the mill. In addition, TIPA+HCl at the two protonation rates allows an increase in mill capacity and in the specific surface area of the cement compared with TIPA, the effect being greater the higher the protonation rate. The use of an amine in the form of a hydrochloric acid salt therefore allows improved mill performance with an effect that can be modulated according to protonation rate. Finally, the mechanical properties of the cement are not modified through the addition of TIPA+HCl at the different protonation rates. At 2-days, the compressive strengths of the cements with additives are equivalent to those of the reference. At 7-days, a slight gain in compressive strength is recorded through the TIPA activating effect, an effect that is seen in its non-protonated form, at 50 weight % protonation and 100 weight % protonation.

TABLE-US-00002 Blaine Pressure (mBar) Mill specific at filter Dosage capacity surface area inlet - mill 2-day CS 7-day CS Description (ppm) (kg/h) (cm.sup.2/g) outlet (MPa) (MPa) Reference  0 178 4017 2.9 35.6 51.6 TIPA (0 weight % 400 195 3915 4.1 35.3 53.4 TIPA protonation) TIPA + HCl  438* 201 3937 3.8 35.7 53.1 (50 weight % TIPA protonation) TIPA + HCl  476** 211 3994 3.7 34.6 52.5 (100 weight % TIPA protonation) *Equivalent to 400 ppm TIPA + 38 ppm HCl **Equivalent to 400 ppm TIPA + 76 ppm HCl.

[0087] This example evidences the fact that in the vertical mill, the use of TIPA in partial hydrochloric acid salt form (TIPA+HCl) instead of TIPA, allows grinding efficacy to be improved translating as a reduction in the differential pressure of the filter, an increase in the specific surface area of the cement and an increase in mill capacity. The higher the protonation rate of TIPA by hydrochloric acid, the more this beneficial effect on mill performance is visible. In addition, the mechanical properties of the cement remain equivalent to that of the reference at 2 days and even slightly higher than the reference at 7 days in the presence of TIPA+HCl (at 50 and 100 weight % protonation).