KR20220104191A - Novel process for high-performance cement - Google Patents

Abstract

The present invention relates to a novel process for the production of high-performance cement, a novel grinding aid composition comprising ester and/or ether polycarboxylate, a process for the preparation of such composition and the use of such composition in the production of cement with or without other additives. It's about use. The present invention provides a novel aqueous composition comprising at least one polycarboxylate polymer and at least one surfactant for use as grinding aid in the manufacture of high performance cement.

Description

Novel process for high-performance cement

The present invention relates to a novel process for the production of high-performance cement, a novel grinding aid composition comprising esters and/or ether polycarboxylates, a process for the preparation of such compositions and a method for preparing cement with or without other additives. to the use of such compositions.

For the production of ordinary cement, preferably Portland cement, clinker is produced by first grinding at high heat a mixture of silica, alumina and limestone containing materials in a rotary kiln. The high fever is above 1.400 °C. The clinker and gypsum are then ground in a suitable mill to produce cement. 27 types of cement are listed in DIN-EN 197-1.

Cement production is accompanied by the release of significant amounts of carbon dioxide, which occurs due to energy consumption in the rotary kiln during clinker production and also due to the calcination of limestone. For example, during the production of 1 ton of cement, 1 ton of carbon dioxide may be released. Thereby, in the prior art, the emission of carbon dioxide is attempted to be reduced through reduction of clinker production. If the amount of clinker is reduced by about 35%, carbon dioxide emissions from cement production can be reduced. Instead of clinker, mineral additives are added to the cement. However, the low content of clinker and the high content of mineral additives lower the required specifications of cement and concrete, such as strength, hardness and setting time.

In order to accelerate the grinding or milling process to minimize energy use, the use of additives is known in the prior art. These additives may be plasticizers, retarders, accelerators and/or stabilizers, and are generally used to increase the efficiency of the grinding step of cement production by lowering the energy used. For example, US Pat. No. 2,673,810 discloses that potassium nitrate is an effective retardant. Organic amines such as trialkanolamine are examples of accelerators used in the grinding of clinker as disclosed in "Cement and Concrete Research", Ramachandran (1973). Polycarboxylates are also used as grinding aids during the production of cement.

These additives can lead to changes in cement specifications while improving energy utilization. However, there is still a need in the art for new methods and compositions to provide stronger, cost-effective and ecological concrete while reducing carbon dioxide emissions.

Accordingly, a main aspect of the present invention is to provide a method for producing high-performance cement by introducing together or separately an aqueous composition of a polycarboxylate polymer and an additive composition into the grinding of cement clinker.

In another aspect, the present invention provides a grinding aid composition for use in the manufacture of high performance cement, wherein the composition comprises a first additive comprising at least one organic amine and at least one amino alcohol, and at least one alkanolamine and at least one A composition is provided comprising a second additive comprising one glycol.

In a further aspect, the present invention provides a grinding aid composition for use in the manufacture of high performance cement, wherein the composition is an aqueous composition comprising at least one polycarboxylate polymer and at least one surfactant. do.

In another aspect, the present invention provides a method for producing a high performance cement comprising the steps of;

a) mixing at least one organic amine and at least one amino alcohol to provide a first additive;

b) mixing at least one alkanolamine and at least one glycol to provide a second additive;

c) mixing the first additive with the second additive to obtain an additive composition;

d) providing an aqueous composition of polycarboxylate polymer comprising at least one surfactant, and

e) introducing the additive composition and the aqueous composition of the polycarboxylate polymer together or separately into the grinding of cement clinker.

In another aspect, the present invention is a high-performance cement obtained by the process according to the invention, wherein the cement comprises from 5 to 45% of mineral additives, or preferably from 10 to 35% of mineral additives, based on the weight of the cement. to provide high-performance cement.

The present invention provides a novel aqueous composition for use as a grinding aid in the manufacture of high performance cement, wherein the composition comprises at least one polycarboxylate polymer and at least one surfactant.

According to the present invention, the surfactant may be a nonionic surfactant, such as a modified fatty alcohol or a nonionic fatty acid ester. The surfactant may also include 1 to 10% glycol.

As used herein, "polycarboxylate polymer" means a polymer having a carboxyl group. The polycarboxylate polymer can be obtained by a polymer-like reaction.

The polycarboxylate polymer according to the invention may be a polycarboxylate ether or polycarboxylate ester polymer.

Polycarboxylate polymers with added surfactants have been found to improve grinding efficiency and strength of cement. The dispersibility of the cement clinker during grinding is improved by the addition of the polycarboxylate polymer composition according to the invention. In addition, these compositions used as grinding aids result in reduced energy consumption.

According to the present invention, the aqueous composition of the polycarboxylate polymer is obtained by diluting the polycarboxylate polymer by mixing it with non-ionized water and a surfactant for 30 to 40 minutes. The dilution is preferably carried out at 30°C.

The present invention also provides a novel high performance cement manufacturing method comprising the steps of;

a) mixing at least one organic amine and at least one amino alcohol to provide a first additive;

b) mixing at least one alkanolamine and at least one glycol to provide a second additive;

c) mixing the first additive with the second additive to obtain an additive composition;

d) providing an aqueous composition of a polycarboxylate polymer according to any one of claims 1 to 5, and

e) introducing the additive composition and the aqueous composition of the polycarboxylate polymer together or separately into cement grinding.

It has been found that the novel process according to the invention provides an increased amount of substitution of minerals and additives for clinker.

The second additive is prepared by mixing at least one alkanolamine and at least one glycol in a reactor. The temperature of the mixing step of the alkanolamine and glycol is preferably 30°C to 50°C, most preferably 40°C. The mixing time of the alkanolamine and glycol is preferably 1 hour to obtain a homogeneous mixture.

According to the present invention, the first additive and/or the second additive may further comprise a nonionic surfactant. The surfactant is 0.1% to 0.5%, preferably 0.2% to 0.3%, by weight of the grinding aid composition.

The amino alcohols according to the invention are 1-(N,N-bis(2-hydroxyethyl)amino)propan-2-ol (diethanolisopropanolamine, also known as DEIPA), ethanolamine, diethanolamine, triethanolamine , N-butyldiethanolamine, M-methyldiethanolamine, diaminomethanol (urea), N-ethyldiethanolamine, diisopropanolamine, methyl diisopropanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanol amines and combinations thereof. A preferred amino alcohol is diethanolisopropanolamine (DEIPA). The aminoalcohol is present in an amount of 30% to 50% by weight of the first additive.

The organic amine according to the present invention is 2-ethyldiisopropylamine (DIPEA/EDIPA), diethylamine, triethylamine, dimethylamine pyridine, ethyldiisopropylamine, procaine, dibenzylamine, N-methylmorpholine , dihydroabiethylamine, 1-ephenamine, methyl-piperidine, and combinations thereof. A preferred organic amine is 2-ethyldiisopropylamine (DIPEA). The organic amine is present in an amount of 50 to 70% by weight of the first additive.

The alkanolamine according to the present invention is 2,2,2-nitrilotriethanol (triethanolamine), 1,1,1-nitrilopropan-2-ol (triisopropanolamine), diethanolamine, diethoxylated isopropyl amines and combinations thereof. A preferred alkanolamine is triethanolamine. The alkanolamine is present in an amount of from 70 to 90% by weight of the second additive.

The glycol according to the present invention is 2-(hydroxyethoxy)ethan-2-ol (diethylene glycol), ethylene glycol, propylene glycol, glycerol (propane-1,2,3-triol), polyethylene glycol, monopropylene glycols and combinations thereof. Preferred glycols are glycerol and/or diethylene glycol. The glycol is present in an amount of 10 to 30% by weight of the second additive.

According to the present invention, the first additive may further comprise diaminomethanal (urea). The amount of urea used in the production process is 5% to 25% by weight, preferably 10% to 20% by weight, based on the weight of the first additive.

The step of mixing the first and second additives is carried out at 30 to 65 °C, preferably 40 to 60 °C.

According to the invention, the ratio of the first additive to the second additive is from 1:0.5 to 4:1.

Surprisingly, it has been found that the process according to the invention allows the grinder to grind clinker into smaller sizes in a shorter time with less energy. Reducing the amount of energy required can significantly reduce the carbon dioxide emissions from cement clinker production by replacing the mineral(s). Polycarboxylate polymer compositions and methods having a density of 1.0 to 1.10 g/cm ³ and a pH of 7 to 9 also provide cements having increased 1-day, 2-day, 7-day and 28-day compressive strength. do.

The method may further comprise adding other additives such as retarders, corrosion inhibitors, desiccants, glidants, defoamers, cryoprotectants and water reducing agents during or prior to grinding.

A mixture of the polycarboxylate polymer composition and the first and second additives in the method for producing high performance cement may be defined as a grinding aid and a cement chemical admixture composition. These admixture compositions are suitable for use in conventional grinding mills such as ball grinders or roller grinders. Therefore, grinding of cement clinker is carried out in a grinding grinder.

Accordingly, in another embodiment, the present invention provides the use of an aqueous composition of a polycarboxylate polymer according to the invention and a mixture of a first additive and a second additive in the manufacture of cement as grinding aid. The composition increases the normal setting time and normal compressive strength of the cement and concrete mixture. Intensity intensifies on the first day in the short term and after 28 days in the long term.

According to the present invention, the test can be performed against standard tests of the prior art, such as EN 197-1, EN 197-2 or ASTMC150/150 M-18. More specifically, EN196-7, EN 196-2, EN 196-3, EN 196-6, EN 196-1 or ASTM C595/C595M, ASTM C109/C109M, ASTM C150.

The cement may further comprise a mineral additive selected from the group consisting of siliceous fly ash, calcareous fly ash, blast furnace slag, limestone (calcium carbonate), silicon dioxide (silica sand), natural pozzolan, industrial pozzolan and burnt shale. have. The type of cement is determined by the type and proportion of the cement composition. Accordingly, a total of 27 types of cement are prescribed. The basic cement types are Portland cement (CEM I), Portland composite cement (CEM II), blast furnace cement (CEM III), pozzolan cement (CEM IV), hydraulic cement, slag cement or composite cement (CEM V). According to the present invention, the cement is preferably Portland cement or the like.

Clay and limestone are raw materials for the production of clinker, a hydraulic compound mainly used in cement production. Clinkers include tricalcium silicate, calcium silicate which may be dicalcium silicate, tricalcium aluminate and aluminoferrite.

In one embodiment of the present invention, the cement may further comprise micro and nanoparticles of nano-sized minerals such as silica, aluminum and ferrite oxides.

Nano-sized minerals or additives may be added to the high-performance cement obtained by the method according to the invention. As described above, the process carried out by adding the additive composition according to the present invention allows the cement to be well pulverized and the cement to be mixed with the nano-sized minerals.

The clinker process according to the invention is a conventional process using a rotary kiln. Cement raw materials, such as calcareous materials, are first ground into a fine powder. They are then introduced into a kiln in which the above raw materials are mixed to produce a uniform composition, and heated at 1000°C - 1500°C, preferably 1350°C - 1450°C. Finally, the mixture, which can be termed clinker, is cooled in a cooler.

Thus, the process for producing cement comprises grinding clinker in the presence of an aqueous composition of polycarboxylate polymer according to the invention and a mixture of first and second additives. Thus, it is possible to reduce the amount of clinker in the cement, which provides a reduction in specific energy consumption and CO ₂ emissions.

The amount of grinding aid in the cement is from 100 to 3000 g/ton, preferably from 500 to 2500 g/ton, based on the weight of the cement.

The clinker is introduced into a grinding device and grinding is effected until the desired cement fineness is obtained. The degree of fineness of the cement containing the grinding aid of the present invention is 2000 to 10000 g/cm ² , preferably 3000 to 6000 g/cm ² , more preferably 3500 to 4500 g/cm ² .

The addition of the polycarboxylate polymer composition and/or the first and second additive mixtures can be effected by spraying onto the clinker. Spraying is carried out by means of a conventional dosing pump.

According to the invention, the mixture of the polycarboxylate polymer composition and the first and second additives may be added separately to the clinker phase. In addition, the first additive and the second additive may be added separately without mixing to the clinker to perform the grinding step.

In the grinding of the cement production process, gypsum may be added together with clinker. Gypsum is a sulfate mineral containing calcium sulfate dihydrate. Gypsum is added during grinding to control the setting time.

In the method for producing cement, this grinding aid composition is 0.1% to 5% by weight, preferably 0.3% to 2.5% by weight of the cement.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

The invention will now be particularly described in conjunction with the following exemplary embodiments; However, the scope of the present invention is not intended and should not be limited to the examples illustrated below.

Example

Example 1

mixture of first additive and second additive

ingredient content (gr) diaminomethanol 10 Diethanolisopropanolamine 12.5 2-ethyldiisopropylamine 12.5 triethanolamine 5 glycerol 4 diethylene glycol 5 modified fatty alcohol One water 50

Method for making grinding aid

- mixing water and urea at 40 ° C;

- adding diethanolisopropanolamine, 2-ethyldiisopropylamine and a surfactant to the mixture of urea to obtain a first additive,

- mixing water, triethanolamine, diethylene glycol and glycerol to obtain a second additive,

- reacting the first additive formulation with the second additive formulation at 50°;

- adding a mixture of the first and second additive polycarboxylate esters.

Aqueous Compositions of Polycarboxylate Polymers

ingredient content (gr) Surfactants 50 Polycarboxylate Ether Polymer (PCE) 500 water 500

Process for preparing aqueous compositions of polycarboxylate polymers

- providing a polycarboxylate polymer synthesized by etherification of a carboxylated acrylic acid monomer;

- diluting the polycarboxylate polymer with non-ionic water and a non-ionic surfactant in a mixer at 30° C. for 40 minutes. (pH is neutral at 7)

Examples of cement prepared using a mixture of first and second additives and a composition of polycarboxylate polymer:

The mixture and composition are introduced together during cement grinding.

Cement Example 1

Component (CEM II/A-S 42.5R) content (percentage) Clinker (K) %80 Blast Furnace Slag (S) %13 Limestone (L) %7 mineral %5

Cement Example 2

Component (CEM II/A-V 42.5R-SR) content (percentage) Clinker (K) %65 Fly Ash (V) %27 Limestone (L) %8 mineral %5

Cement Example 3

Component (CEM I 42.5R) content (percentage) Clinker (K) %95 mineral %5

Cement Examples 1 to 3 were compared with the same cement prepared without using the grinding aid composition of the present invention, and the results in the table below illustrate the effect of grinding clinker with the grinding aid composition according to the present invention. Testing is performed using standard ASTM C150.

CEM I 42.5R CEM II/A-S 42.5R CEM IV/A-V 42.5R-SR %91K+%5 L+%4 M %78K+%12S+%5L+%4M %67K+%24V+%5L+%4M MPa R-CEMI ECO CEM I R-CEM II ECO CEM II R-CEM IV ECO CEM IV 1 day 20,1 35,7 18,9 25,8 16,3 28,0 2 days 32,3 43,5 29,6 38,8 27,0 44,5 7 days 44,5 50,4 39,8 45,0 36,5 53,8 28 days 52,3 61,0 51,0 55,1 50,4 65,8 Fineness (g/cm ² ) 3699 3681 4194 4356 4210 4304

Claims (24)

An aqueous grinding aid composition for use in the manufacture of high performance cement, comprising:
An aqueous grinding aid composition comprising at least one polycarboxylate polymer and at least one surfactant. According to claim 1,
wherein the polycarboxylate polymer is a polycarboxylate ether or polycarboxylate ester polymer. 3. The method of claim 1 or 2,
An aqueous grinding aid composition, wherein the polycarboxylate polymer has a molecular weight of 2000 to 50000. 4. The method according to any one of claims 1 to 3,
wherein the surfactant is nonionic. 5. The method according to any one of claims 1 to 4,
wherein the surfactant is present in an amount of 0.1% to 0.3% by weight of the composition. 6. The method according to any one of claims 1 to 5,
The aqueous grinding aid composition is obtained by diluting the polycarboxylate polymer by mixing it with non-ionic water and a surfactant for 30 to 40 minutes. 7. Use of the aqueous grinding aid composition according to any one of claims 1 to 6, comprising:
Use in the manufacture of high-performance cement. A method for manufacturing high-performance cement, comprising:
a) mixing at least one organic amine and at least one amino alcohol to provide a first additive;
b) mixing at least one alkanolamine and at least one glycol to provide a second additive;
c) mixing the first additive with the second additive to obtain an additive composition;
d) providing an aqueous composition of a polycarboxylate polymer according to any one of claims 1 to 5, and
e) introducing the additive composition and the aqueous composition of the polycarboxylate polymer together or separately into the grinding of the cement;
A method comprising 9. The method of claim 8,
The method of claim 1, wherein the first additive and the second additive further comprise at least one surfactant. 10. The method of claim 9,
wherein the surfactant is nonionic. 11. The method according to any one of claims 8 to 10,
wherein the first additive is provided by mixing at least one organic amine, at least one amino alcohol and sodium gluconate. 12. The method according to any one of claims 8 to 11,
The organic amine is 2-ethyldiisopropylamine, diethylamine, triethylamine, dimethylamine pyridine, ethyldiisopropylamine, procaine, dibenzylamine, N-methylmorpholine, dihydroabiethylamine, 1 -ephenamine, methyl-piperidine and combinations thereof. 13. The method of claim 12,
wherein the organic amine is 2-ethyldiisopropylamine. 14. The method according to any one of claims 8 to 13,
wherein the organic amine is present in an amount of 35% to 50% by weight of the first additive. 15. The method according to any one of claims 8 to 14,
The amino alcohol is 1-(N,N-bis(2-hydroxyethyl)amino)propan-2-ol (diethanolisopropanolamine, DEIPA), ethanolamine, diethanolamine, triethanolamine, diaminomethanol ( urea), N-butyldiethanolamine, M-methyldiethanolamine, N-ethyldiethanolamine, diisopropanolamine, methyl diisopropanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, and combinations thereof A method selected from the group consisting of. 16. The method of claim 15,
wherein the amino alcohol is 1-(N,N-bis(2-hydroxyethyl)amino)propan-2-ol (DEIPA). 17. The method according to any one of claims 8 to 16,
The glycol is 2-(hydroxyethoxy)ethan-2-ol (diethylene glycol), ethylene glycol, propylene glycol, glycerol (propane-1,2,3-triol), polyethylene glycol, monopropylene glycol and these selected from the group consisting of a combination of 18. The method of claim 17,
wherein the glycol is glycerol and/or diethylene glycol. 19. The method according to any one of claims 8 to 18,
Step c) is carried out at 30 to 65 °C. 20. The method of claim 19,
The process according to any one of the preceding claims, wherein reaction step c) is carried out at 40 to 60°C. 21. The method according to any one of claims 8 to 20,
wherein the ratio of the first additive to the second additive is from 1:0.5 to 4:1. 21. A high-performance cement obtained by the method according to any one of claims 8 to 20, comprising:
Wherein the cement comprises 5 to 45% of mineral additives based on the weight of the cement. 22. The method of claim 21,
The high performance cement comprises 10 to 35% of mineral additives based on the weight of the cement. 23. The method of claim 21 or 22,
wherein said mineral additive is selected from the group consisting of siliceous fly ash, calcareous fly ash, blast furnace slag, limestone (calcium carbonate), silicon dioxide (silica sand), natural pozzolan, industrial pozzolan and combusted shale.