DEGRADED AMINE SOLUTION AS PERFORMANCE ENHANCER

Abstract

A method for recycling an amine reclaimer waste composition obtained during reclaiming of an amine scrubbing solution has the steps of extracting carbon dioxide from an exhaust gas with an amine scrubbing solution, reclaiming the amine scrubbing solution wherein the amine reclaimer waste composition is obtained, and adding the amine reclaimer waste composition as a grinding aid to a binder component or as an admixture for enhancing the strength development and/or workability of a binder to the binder or a hydraulic building material made with the binder. A method for manufacturing a binder for manufacturing building materials uses the amine reclaimer waste composition.

Claims

1. (canceled)

2: A method for recycling of an amine reclaimer waste composition comprising the steps: extracting carbon dioxide from an exhaust gas with an amine scrubbing solution, reclaiming the amine scrubbing solution wherein the amine reclaimer waste composition is obtained, and adding the amine reclaimer waste composition as a grinding aid to a binder component or as an admixture for enhancing the strength development and/or workability of a binder to the binder or a hydraulic building material made with the binder.

3: The method according to claim 2, wherein the step of reclaiming of the amine scrubbing solution comprises distillation and the amine reclaimer waste composition is obtained as bottom fraction from the distillation.

4: The method according to claim 2, wherein the amine scrubbing solution comprises an amine selected from monoethanolamine, diethanolamine, triethanolamine, diisopropylamine, aminoethoxyethanol, 2-amino-2-methylpropan-1-ol, methyldiethanolamine, piperazine, hexane-1,6-diamine, and mixtures of two or more thereof.

5: The method according to claim 2, wherein the amine reclaimer waste composition has a hydroxyl value in the range from 5 to 1000 mg KOH/g.

6: The method according to claim 2, wherein the amine reclaimer waste composition has a nitrogen content in the range from 0.1 to 20% by weight based on the total amine reclaimer waste composition.

7: The method according to claim 2, wherein the binder is a hydraulic binder and/or the binder component is a cement clinker, a cement, a supplementary cementitious material, and/or a filler.

8: The method according to claim 7, wherein the cement is a cement as defined and classified in DIN EN 197-1:2011, DIN EN 197-5:2021, DIN EN 413-1:2011, DIN EN 15368:2010, and DRAFT EN 197-6:2022, and/or the clinker is Portland cement clinker, and/or the supplementary cementitious material is a cement component as defined and classified in DIN EN 197-1:2011, DIN EN 197-5:2021, DIN EN 413-1:2011, DIN EN 15368:2010, and DRAFT EN 197-6:2022, and/or the filler is a filler as defined and classified in DIN EN 197-1:2011, DIN EN 197-5:2021, DIN EN 413-1:2011, DIN EN 15368:2010, DRAFT EN 197-6:2022, or a side product from aggregate production.

9: The method according to claim 2, wherein the amine reclaimer waste composition comprises at least one amine selected from the group consisting of a) amines of the formula (I): NR.sup.1R.sup.2R.sup.3, wherein R.sup.1 is selected from C.sub.1-C.sub.6 alkyl and C.sub.2-C.sub.6 hydroxyalkyl R.sup.2 is selected from formyl, acetyl, carboxyl, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkyl carbonyl, C.sub.1-C.sub.6 hydroxyalkyl, C.sub.2-C.sub.6 alkylamine, C.sub.2-C.sub.6 alkylamino-C.sub.2-C.sub.6 alkylamine, and carbamoyl-C.sub.2-C.sub.6-hydroxyalkyl R.sup.3 is selected from H and C.sub.1-C.sub.6 alkyl b) 5- to 7-membered saturated heterocycles having at least one nitrogen atom in the ring, which can comprise one or two further hetero atoms as ring members selected from NR.sup.x, O, S, SO and SO.sub.2, wherein the heterocycle is unsubstituted or substituted by 1, 2, or 3 identical or different substituents selected from C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 hydroxyalkyl, C.sub.2-C.sub.6 alkylamine and oxo; and R.sup.x is selected from hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 hydroxyalkyl, C.sub.2-C.sub.6 alkylamino-C.sub.2-C.sub.6 hydroxyalkyl, and C.sub.2-C.sub.6 alkylamin; c) amines from the amine scrubbing solution; and d) mixtures thereof.

10: The method according to claim 2, wherein the amine reclaimer waste composition comprises one or more of hydroxyethylimidazolidone, cyclic urea of 1-(2-((2-hydroxyethyl)amino)-ethyl)imidazolidin-2-one), hydroxyethylethylenediamine, monoethanolamine trimer, ammonium salts, ethylenediamine, 2-imidazoline, formate salts, acetate salts, 1-amino-ethyl-piperazine, N-hydroxyethyl-piperazine, 1-ethyl-piperazine, 1-methyl-piperazine, 1,4-dimethyl-piperazine, diethanolamine, N-methyl-aminoethanol, 1-formyl-piperazine, hydroxyethyl formamide, oxalate salts, oxylamide, nitrate salts, nitrite salts, hydroxyethylimidazole, N-(2-hydroxyethyl)-glycine, N-nitroso-piperazine, bicine, oxazolidin-2-one, N-(2-hydroxyethyl)imidazolidin-2-one, N,N-bis-(2-hydroxyethyl)urea, N-(2-hydroxyethyl)-diethylenetriamine, N-[2-[(2-hydroxyethyl)amino]ethyl]-imidazolidin-2-one, N-(2-aminoethyl)-N-(2-hydroxyethyl)imidazolidin-2-one, N,N-bis(2-hydroxy-ethyl)imidazolidin-2-one, glycine, glycolic acid, oxalamide, oxamic acid, N-(2-hydroxyethyl)formamide, oxalic acid, N-(2-hydroxyethyl)acetamide, 2-Hydroxy-N-(2-hydroxyethyl)acetamide, N-glycylglycine, N-(2-hydroxyethyl)oxamic acid, N-(2-hydroxyethyl)piperazin-2-one, N-(2-hydroxyethyl)piperazin-3-one, N-bis(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)-2-(2-hydroxyethyl-amino)acetamide, N,N-bis(2-hydroxyethyl)oxalamide, 2-(Methylamino)ethanol, N-(2-hydroxyethyl)-succinimide, N,N,N-tris(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)aziridine, N-(2-hydroxyethyl)oxazolidin-2-one, N,N-bis(2-hydroxyethyl)ethylenediamine, Triethanolamine, N,N-bis(2-hydroxyethyl)-piperazine, N,N,N-tris(2-hydroxy-ethyl)ethylenediamine, Bis-(2-(2-hydroxyethylamino)ethyl)ether, N-(2-hydroxyethyl)-N-(2-(2-hydroxyethylamino)-ethyl)piperazine, N-2-[bis(2-hydroxyethyl)-amino]ethylpiperazine, N-2-[bis(2-hydroxyethyl)-amino]ethyloxazolidin-2-one, N,N,N,N-tetrakis(2-hydroxyethyl)urea, N,N,N,N-tetrakis(2-hydroxyethyl)ethylenediamine, N-2-[bis(2-hydroxyethyl)-amino]ethyl-N-(2-hydroxyethyl)piperazine, N,N,N,N-tetrakis(2-hydroxyethyl)-diethylenetriamine, N,N,N,N-tetrakis(2-hydroxyethyl)-diethylenetriamine, Monoethanolamine, N-methyldiethanolamine, N,N-bis(2-hydroxyethyl)piperazine, N,N,N-tris(2-hydroxyethyl)ethylenediamine, Ethylene glycol, N,N-(dimethyl)ethanolamine, N-methylmorpholine, Diethanolamine, N,N-dimethylpiperazine, N-(2-hydroxyethyl)oxazolidin-2-one, N-(2-hydroxyethyl)-N-methylpiperazine, N,N-bis(2-hydroxyethyl)-piperazine, N-[2-(2-hydroxyethyl-methylamino)ethyl]-N-methylpiperazine, N-methyl-N,N,N-tris(2-hydroxyethyl)-ethylenediamine, N-[2-2-hydroxyethylmethylamino)ethyl]-N-(2-hydroxyethyl)-piperazine, N,N,N,N-tetrakis(2-hydroxyethyl)ethylenediamine, N-methylmorpholin-2-one, N-methylmorpholin-2,6-dione, 2-[Methyl(2-hydroxyethyl)-amino]acetic acid, N,N-trimethyl-N-(2-hydroxyethyl)ethylenediamine, Ethyl enediamine, Imidazolidin-2-one, N-methylpiperazine, N,N-dimethylpiperazine, N-formylpiperazine, N-ethylpiperazine, N-(2-hydroxyethyl)-N-methyl piperazine, N-(2-hydroxyethyl)piperazine, N,2,2-trimethylethanolamine, 4,4-Dimethyloxazolidin-2-one, N,4,4-trimethyloxazolidin-2-one, 4,4-Dimethyl-1-hydroxytertisobutyl-imidazolidin, 1,3-Bis-(2-hydroxy-1,1-dimethylethyl)urea, 2,4-Lutidine, Diglycolamine, 2-Hydroxylmethylpiperidine, Diethylenetriamine, Piperidine, Hexamethyleneimine, Homopiperazine, and Hexamethylenediamine.

11: A method for manufacturing a binder comprising the steps: i) providing at least one component of the binder, ii) providing an amine reclaimer waste composition by extracting carbon dioxide from an exhaust gas with an amine scrubbing solution and reclaiming the amine scrubbing solution to provide the amine reclaimer waste composition, iii) blending the amine reclaimer waste composition with the at least one component, and iv) grinding the amine reclaimer waste composition blended with the at least one component to provide the binder, with the proviso that a cement is additionally blended with the ground amine reclaimer waste composition blended with the at least one component in case the at least one component in step i) is not a cement.

12: The method according to claim 11, wherein the amine reclaimer waste composition is dried before step iii) or the amine reclaimer waste composition blended with the at least one component is dried after step iii).

13: The method according to claim 11, wherein the binder obtained in step iv) has a Blaine fineness from 2000 to 15000 cm.sup.2/g determined according to DIN EN 196-6:2019 Chapter 4, or a d(90) below 100 m determined by laser diffraction according to ISO 13320:2020, or a sieve residue on a 90 m sieve of below 5% by weight determined according to DIN EN 196-6:2019 Chapter 5.

14: The method according to claim 11, wherein the binder comprises from 4.9 to 99.9% by weight of cement and from 0.001 to 3% by weight of amine reclaimer waste composition.

15: The method according to claim 14, wherein the binder additionally comprises from 5 to 95% by weight of one or more supplementary cementitious material(s) and/or from 1 to 50% by weight of one or more fillers and/or up to 5% by weight minor additional components as defined in EN 197-1 and EN 197-5 and/or up to 5% by weight additives and/or admixtures and/or from 1 to 50% by weight recycled concrete fines as described in DRAFT EN 197-6:2022 and/or from 1 to 50% by weight carbonated recycled concrete fines.

16. (canceled)

17: The method according to claim 5, wherein the amine reclaimer waste composition has a hydroxyl value in a range from 50 to 750 mg KOH/g.

18: The method according to claim 5, wherein the amine reclaimer waste composition has a hydroxyl value in a range from 100 to 500 mg KOH/g.

19: The method according to claim 6, wherein the amine reclaimer waste composition has a nitrogen content in a range from 0.5 to 10% by weight based on the total amine reclaimer waste composition.

20: The method according to claim 6, wherein the amine reclaimer waste composition has a nitrogen content in the range from 2 to 8% by weight based on the total amine reclaimer waste composition.

21: The method according to claim 3, wherein the binder is a hydraulic binder and/or the binder component is a cement clinker, a cement, a supplementary cementitious material, and/or a filler.

22: The method according to claim 11, wherein the binder comprises from 4.9 to 99.9% by weight of cement and from 0.01 to 1% by weight of amine reclaimer waste composition.

23: The method according to claim 11, wherein reclaiming of the amine scrubbing solution comprises distillation and the amine reclaimer waste composition is obtained as bottom fraction from the distillation.

24: The method according to claim 11, wherein the at least one component is a cement clinker, a cement, a supplementary cementitious material, and/or a filler.

25: The method according to claim 24, wherein the binder comprises from 4.9 to 99.9% by weight cement and from 0.001 to 3% by weight amine reclaimer waste composition.

Description

[0073] In the figures:

[0074] FIG. 1 shows the specific heat measured during hydration of binders according to the invention. The heat of hydration was determined acc. to DIN EN 196-11.

[0075] FIG. 2 shows the relative Blaine fineness of ground clinker according to the invention. The Blaine fineness was determined acc. to DIN EN 196-6.

[0076] FIG. 3 shows the relative d(90) value of a clinker ground according to the invention. The d(90) value is a parameter generated from a particle size distribution analysis. The particle size distribution analysis was performed according to ISO 13320 in Isopropanol as dispersion agent. A d(90) value of e.g. 50 m means that 90% of the sample is smaller than 50 m. Hence in the present example a relative d(90) value <100% means that the ground clinker is finer than the reference.

EXAMPLE 1

[0077] A simulated amine reclaimer waste composition (Mix1) was made from 10% by weight hydroxyethylimidazolidone (HEIA), 50% by weight N-(2-hydroxyethyl)-glycine (HEGly), 20% by weight hydroxyethyl formamide (HEF), 10% by weight sodium sulfate and 10% by weight sodium oxalate. Mix1 had a hydroxyl value of 360, a nitrogen content of 10 wt.-% and was dissolved in water. The obtained clear solutions were added to a cement CEM II/A-LL 32.5 R (acc. to DIN EN 197-1) as mixing water at a water to binder ratio of 0.4 according to EN 196-11. The cement had a sieve residue on a 90 m sieve of 0.92% by weight, a Blaine fineness of 3780 cm.sup.2/g, and a d(90) of 63.4 m. The investigated active components were dosed at a solid content to binder ratio of 0.083% by weight and selected constituents of reclaimer waste at 0.024% by weight to obtain binders according to the invention. Mix1 represents the simulated reclaimer waste composition. Additionally, the pure amine components of Mix1, oxazolidin-2-one (OZD) and piperazine (Pz) were tested. A reference binder was provided with the addition of triethanolamine (TEA) as state of the art performance enhancer. Hydration took place in a sealed glass ampule directly in the calorimeter. FIG. 1 shows the cumulative heat flow measured during hydration for the first three days at a dosed content of 0.083% by weight. FIG. 2 shows the cumulative heat flow measured during hydration for the first three days at a dosed content of 0.024% by weight. The cumulated heat flow on day 3 is listed in table 1.

TABLE-US-00001 TABLE 1 cumulative heat [J/g] at a dosage of added material 0.083% 0.024% Mix1 260 not tested HEIA 261 not tested HEGly 264 256 HEF 258 256 OZD 262 not tested Pz 251 253 TEA 262 252

[0078] The results in the FIGS. 1 and 2 and table 1 show that the binders comprising the simulated amine reclaimer waste composition or components thereof developed similar heat, i.e. hydration proceeded similar as that of the reference binder with a state of the art performance enhancer. This correlates with a similar strength development and early strength compared to a binder without enhancer. Thus, the amine reclaimer waste is a useful performance enhancer for binders.

EXAMPLE 2

[0079] Different typical components of amine reclaimer waste compositions, i.e. pure chemicals, were added as solution in water to a portland cement clinker in an amount of 0.1% by weight. The solutions had a concentration of 33% by weight so that the concentration of solid active ingredient with respect to clinker was 0.03% by weight. As reference a clinker was mixed with 0.1% by weight of water. The clinker chemistry determined as described in DIN EN 196-2:2013 as well as the mineralogical composition determined as described in DIN EN 13925-2:2003 is shown in table 2. The clinkers with addition and the one without as reference were then ground in a planetary ball mill. Grinding time was kept constant for all grindings. FIG. 3 depicts the achieved Blaine fineness relative to that of the reference clinker without added amine reclaimer waste composition but only water. FIG. 4 shows the respective d(90) values relative to that of the reference clinker. It is apparent that the amine reclaimer waste components are effective grinding aids. The achieved Blaine fineness could be increased and the d(90) value decreased when keeping the grinding time constant.

TABLE-US-00002 TABLE 2 Chemistry and mineralogy of clinker [% by weight] LOI 0.18 SiO.sub.2 20.5 Al.sub.2O.sub.3 5 TiO.sub.2 0.35 MnO 0.06 Fe.sub.2O.sub.3 3.12 CaO 65.1 MgO 2.49 K.sub.2O 1.29 Na.sub.2O 0.37 SO.sub.3 1.44 P.sub.2O.sub.5 0.12 C.sub.3S (M1) 15.5 C.sub.3S (M3) 54.6 C.sub.2S (beta) 5.9 C.sub.2S (alpha) 0.3 C.sub.3A (cub) 5.1 C.sub.3A (ortho) 2.2 C.sub.4AF 9.9 mayenite 0.7 free lime 2.2 periclase 1.4 arkanite 0.2 aphthitalite 1.6 syngenite 0.3

EXAMPLE 3

[0080] The clinkers obtained as described in example 2 were blended with a sulphate carrier at an amount of 4% by weight to a CEM I cement as defined and described in DIN EN 197-1. The chemical composition determined according to DIN EN 196-2:2013 is shown in table 3. The heat of hydration of the cements was determined at a water to binder ratio of 0.4 according to EN 196-11. Hydration took place in a sealed glass ampule directly in the calorimeter. FIG. 5 depicts cumulative heat flow after 3 days of hydration relative to the cement obtained by blending the clinker ground with water with the sulphate carrier. It is apparent that the amine reclaimer waste components are effective grinding aids and performance enhancers. The binders comprising reclaimer waste compositions achieved higher heat of hydration values. This correlates with a higher strength development and early strength compared to a binder without enhancer.

TABLE-US-00003 TABLE 3 Chemistry and mineralogy of sulphate carrier [% by weight] LOI 3.92 SiO.sub.2 2.48 Al.sub.2O.sub.3 0.71 TiO.sub.2 0.04 MnO 0.01 Fe.sub.2O.sub.3 0.29 CaO 38.1 MgO 1.56 K.sub.2O 0.19 Na.sub.2O 0 SO.sub.3 52.5 P.sub.2O.sub.5 0 gypsum 1.6 anhydrite 88.8 dolomite 7.6 quartz 2.0