SK288418B6 - Combined binder on the basis of waste material - Google Patents

Abstract

Combined binder on basis of wastes containing Portland siliceous clinker in an amount 5 to 40 % by weight, advantageously 10 to 30 % by weight, and 94,5 to 50 % by weight of ash or mixture of ash and metallurgical slag mixed in optional proportion or mixture of metallurgical slag and alkaline activator, wherein the alkaline activator are alkaline waste waters, leaches from sludge beds of red and brown mud, what is the waste coming from bauxite processing by Bayer method alkaline leaching at production of Al2O3 and aluminum and generated products from the mentioned wastes in an amount with content of alkaline component analytically expressed as 0,01 to 6,5 % by weight of Na2O.

Description

The invention relates to alkaline activated binders, alkaline activated cements, geopolymers, alkaline activated concrete, alkaline activated mortars, building mixtures, materials and products containing alkaline activated binders based on waste and by-products with combined solidification and hardening process, with increased chemical resistance, resistance against low CO ₂ fire.

BACKGROUND OF THE INVENTION

At present, environmental protection is particularly timely. A major problem is the global warming of the Earth's atmosphere, the climate change associated with it, and the accumulation of waste without its efficient recovery.

The greenhouse effect is caused by greenhouse gases, among which the most negative amounts include carbon dioxide _CO2. The source of much of the _CO2 is energy (thermal power plants, heating plants, domestic heating), transportation, industrial activity, production of building binders (cement and lime), ceramic and glass, metals, steel production. In terms of CO ₂ emissions, the silicate industry, and in particular the production of building binders, is a major contributor to undesirable CO ₂ emissions. CO ₂ from cement production accounts for 5-8% of total CO ₂ emissions. Today, the total amount of CO ₂ emitted from the production of 1 tonne of Portland cement is 0.8 tonnes of CO ₂ .

Another major problem is the accumulation of waste, old and emerging landfills as environmental burdens, without the possibility of their recovery. The same problem is the accumulation of by-products of industrial production with low utilization, resp. seasonally disadvantageous consumption.

One of these old environmental burdens is also the heaps, where brown and red sludge from the production of alumina A1 ₂ O ₃ from bauxite by the Bayer method of alkaline leaching with NaOH accumulated for a long time. These are landfills after long-term, several tens of annual production of Al ₂ O ₃ and aluminum, with deposits of several million tonnes, occupying an area of tens of hectares, which can also cause environmental disasters, as was the case in 2005. 2010 in Hungary (Kol. Autorů, Editor-in-Chief Benedek János, Kolontár Report, Causes and Lessons Front of the Red Mud Disaster, Published by Greens, Printing: Cypress Ltd., Budapest, March 2011).

Since brown and red sludge have little use, due to their high alkalinity and heavy metal content, reclamation of their landfills is under way (Ťahúňová, M., Solution of environmental burdens in ZSNP, as, MČ2 / 2009, Enviromagazine, pp. 12 - 14 (2009). The reclamation of the sludge sludges consists in their stripping, which, however, results in the accumulation and circulation of rainwater in the sludge ponds, which in contact with the sludge contaminate with alkalis and become highly alkaline with a pH of up to 13.5. Alkaline waters must be pumped from the tailings pond to be pumped in pools and then treated, as the high alkalinity of these waters does not allow them to be discharged into surface and groundwater. As the capacity of the reservoirs is limited and the weather conditions (rainfall, snow, ice) make the re-emergence of hazardous alkaline waters necessary, their constant treatment is necessary. The treatment may consist of treating them in a physico-chemical manner, e.g. with sulfuric acid H ₂ SO ₄ , electrodialysis followed by separation of low and high salt water streams, concentration of the high salt stream in the evaporators and discharge of the low salt stream into the sewer. Neutralization of alkaline waters is also possible with the use of CO ₂ (Ramesh Chandra Sahu and, Rajkishore Patel, Bankim Chandra Ray, Neutralization of red mud using CO ₂ sequestration cycle, Journal of Hazardous Materials, 179, pp. 28-34, 2010).

In addition to their high alkalinity, the problem of alkaline water treatment is their different chemical composition given by the seasons, weather conditions such as intensity and frequency of precipitation, melting of snow and ice, and thus different concentrations of OH and Na ⁺ .

The high utilization of alkaline waters formed from brown and red sludge and sludge itself is prevented by high Na ⁺ content, high pH and high heavy metal content. Cement, Al ₂ O ₃ and Fe ₂ O ₃ in sludge are interesting for the cement industry, giving them the potential to produce cementitious raw material mixtures, but the presence of Na ₂ O during firing in modern cementitious rotary kilns with a cyclone heat exchanger is a serious obstacle whereas the presence of alkali causes sticking in the kiln system, reduced performance and clogging of the heat exchanger, precalcination systems. Furthermore, increasing the alkali content of Portland cements leads to an increase in the susceptibility of the aggregate to the alkaline-silica reaction in concretes, ie to the alkaline expansion of the aggregate and the destruction of concretes, therefore the alkali content of Portland cements is limited to Na ₂ O + 0,658 K ₂ O <0,6% weight. (STN EN 206-1 / NA).

A solution of JP 2004269304 A is mentioned as the possibility of using red sludge in the production of cement clinker. Here, the red sludge is mixed with the components containing calcium and chlorine. In this solution, the alkaline component is removed from the red sludge and clinker by firing at 1000 ° C. The alkaline chlorides evaporate from the clinker and are removed from the furnace system by a special device, so-called. by-pass. However, by-pass operation leads to economic losses - electricity consumption, heat loss by exhaust gases, cooling of hot flue gases, dust separation - and problems with the use of high alkaline chloride withdrawn dusts, thus creating additional low-waste waste (Schôffmann, H. and Weichinger, M., 5 ^th VDZ Congress, Disseldorf, Germany, pp. 246-251, 2002). Alkaline chlorides in the furnace system also damage corrosion of iron and steel parts, iron anchors fastening the refractory materials in the furnace and heat exchanger, and also the refractory lining itself by chemically aggressive reactions. The residual alkaline chlorides bound in the clinker, which cannot be removed by-pass, increase the chlorides in the cements, which subsequently cause the chloride corrosion of the concrete stone and the steel reinforcement in the reinforced concrete in the concretes, therefore the chloride content Cl in cements must not exceed 0.1 wt. (STN EN 197-1).

Another method for the possible production of cement from red sludge is disclosed in CN 1613809 A, where the red sludge is dealkalized by filtration. However, filtered alkaline water remains a problem.

The use of red sludge in a by-pass dust mixture in the production of hydraulic cement is disclosed in WO 86/05773, wherein the mixture also contains smaller amounts of lime CaO, gypsum CaSO ₄ . 2H ₂ O and Al ₂ O ₃ alumina and heated to 1250-1400 ° C. This makes it possible to produce special sulfoaluminate-belite cement based on clinker minerals 3CA.CaSO ₄ , C ₂ S, C ₄ AF, with the possibility of residual CaSO ₄ and C (C = CaO, S = SiO ₂ , A = Al ₂ O ₃ , F = Fe ₂ O ₃ , M = MgO, N = Na ₂ O, K = K ₂ O, H = H ₂ O).

Further uses of red sludge, natural limestone CaCO ₃ , gypsum and minor admixtures in the production of sulfoaluminate-belite cements are cited in CN 101439938 A and CN 1837121 A and dealkalized red sludge in CN 101891406 A.

CN 1522981 A solution calculates red sludge to produce activated red-colored stone and then cement, a multi-component system consisting of 30 - 60% activated red stone, 2 - 4% gypsum, 3 - 5% iron oxide Fe ₂ O ₃ red and 0.3 - 0.8% additive.

Another environmental problem is the production of some by-products, such as fly ash from metallurgy and energy. The large-scale use of these by-products offers the production of cements and building binders and concrete. However, not all metallurgical slags are suitable for the production of cements and concretes according to the applicable standards (STN EN 197-1, STN EN 15167-1 and STN EN 206-1, STN EN 12620) and also not all fly ash are suitable for the production of cement and concrete according to valid standards (STN EN 197-1, STN EN 450-1 and STN EN 206-1).

Ash is a by-product of electricity and heat production and metallurgical slag is a by-product of iron, steel and non-ferrous metals. The disadvantage of fly ash is its variable chemical, mineralogical and granulometric composition given by the origin and type of coal used and the type of combustion plant. The disadvantage is also the seasonality of fly ash production, when in the winter months their production is highest and the production of cements and concrete is minimal. Unlike conventional fly ash, fly ash from fluidized-bed coal does not comply with the applicable standards (STN EN 197-1, STN EN 450-1 and STN EN 206-1) and virtually all their production must be landfilled. Only some of the siliceous and lime ash are also suitable for the cements themselves (STN EN 197-1) and as a binder - pozzolanic admixture, admixture II. of type also in concrete (STN EN 206-1).

Some metallurgical slags are only suitable for cement production as an ingredient in cementitious raw material mixtures (steel slags, ladle slags, slags from non-ferrous metal production and refining) and as artificial dense aggregates for concrete (blast furnace air-cooled slags, steel slags, slags from production and refining of non - ferrous metals). Only some of the blast furnace granulated debris are also suitable for cements alone (STN EN 197-1) and as a binder - latent hydraulic impurity, impurity II. of type also in concrete (STN EN 206-1).

Ash and metallurgical debris, including those that do not meet the standards for the production of conventional Portland cements, and concretes are suitable for the production of alkaline activated binders - geopolymers. Geopolymers are based on the alkaline activation (aluminosilicates) of materials such as metallurgical slags, in particular blast furnace slag, fly ash, kaolin, metakaolin. For alkaline activation, alkaline activators are used, such as industrially manufactured with high purity sodium hydroxide NaOH, sodium silicate Na ₂ SiO ₃ , Na ₄ SiO ₄ , sodium carbonate Na ₂ CO ₃ , sodium sulfate Na ₂ SO ₄ , less common are equivalent potassium salts and hydroxide (Shi, C. Jimenes, A., F. and Palomo, A., New Cements for the 21st Century: The Pursuit of an Alternative to Portland Cements, Cement and Concrete Research, Vol. 7, pp. 570-763, 2011).

Geopolymers consist of a three-dimensional aluminosilicate lattice, which can be expressed by the empirical formula Me _n [- (SiO ₂ ) _z -AlO ₂ ] n.wH ₂ O, where Me is an alkaline cation which balances the negative charge of A1 (OH) ₄ groups , u is from 1 to 4 and is a measure of the degree of polymerization. Geopolymerization requires high pH = 13 environments at normal temperatures (Davidovits, J., Geopolymer chemistry and sustainable development. The Poly (sialate) terminology: a very useful and simple model for the promotion and understanding of green-chemistry., 4th World Congress Geopolymer 2005, Saint-Quentin, June 29th-July, France, pp. 9-16, 2005).

Geopolymers may have different compositions, different sources of aluminosilicates and different alkaline activating agents. Alkali binder activated with alkali metal salts containing slag, clay, marlin, fly ash according to US 6409819 B1. Alkaline activated binder containing Mg ²⁺ according to KR 101014868 B1. Alkaline activated binder containing ash, slag and sodium without Ba (OH) ₂ and Ca (OH) ₂ to prevent the alkaline-silica reaction of aggregates in concrete according to KR 100942028 B1. Alkaline activated concrete containing slag and anhydrous Na ₂ CO ₃ according to UA 13869 U. Alkaline activated binder containing a complex alkaline activator based on Na ₂ CO ₃ and NaOH according to WO 2011/087304 A2. Alkali activated gel material containing slag and for alkaline activation natural soda sodium carbonate decahydrate Na ₂ CO ₃ .10H ₂ O according to CN 1699252 A. High strength composite cement based on Portland cement clinker and a mixture of aluminosilicates activated with alkaline sulphates such as Na ₂ SO ₄ or K ₂ SO ₄ according to WO 2010/130623 A1. Alkali activated ash and slag based mortar, alkali activated by liquid water glass or sodium silicate according to KR 20100090054 A. Alkali activated binder containing fly ash, blast furnace slag and combinations of Portland cement clinker, natural or artificial pozzolan, thermally activated clay and alkaline activator in sodium or potassium water glass and NaOH or NaOH, optionally also Portland mixed cement or Portland slag cement, or blast-furnace cement according to CZ 289735. Alkaline activated ash-based geopolymer polymer containing SiO ₂ , Al ₂ O ₃ , H ₂ O and Me ₂ 0, wherein Me is a metal ion of the Li, Na, K, Rb and Cs group also suitable for encapsulating hazardous and radioactive materials according to NZ 527772 A.

One disadvantage of conventional geopolymers based on N-A-S-H or K-A-S-H gels is their relatively shorter solidification compared to Portland cements. As the pH alkalinity in the geopolymer mixture increases, the setting time of US 5565028 is shortened. Therefore, solidification retarders, e.g. phosphates as in US 5366547.

A further disadvantage of geopolymers based on N-A-S-H or K-A-S-H gels is the necessity of short-term overheating, at up to about 85 ° C, or autoclaving to consolidate their three-dimensional structure. for the production of concrete.

All these prior solutions, however, require financially demanding, industrially produced, respectively. available natural, chemically high-purity sodium or potassium salts, which significantly overpriced the geopolymeric binders. It would be advantageous to find a simple method of mass disposal and recovery of waste alkaline waters, leachates or their concentrate formed in evaporators, dryers or dry matter; said salts with alkaline waters, leachates, concentrate together with the use of fly ash and metallurgical debris for the production of geopolymer-type building binders at a very low cost.

It would be advantageous to use the wastes to produce alkali-activated binders, alkali-activated cements, geopolymers, alkali-activated concrete, alkaline-activated mortars, building mixtures, materials and products containing alkali-activated binders with lower costs and CO ₂ emissions than commercially available cements.

It is an object of the present invention to design a novel composite binder composition based on mixtures of various wastes and by-products for the production of alkali-activated binders, alkali-activated cements, geopolymers, alkali-activated concrete, alkali-activated mortars, construction mixtures, materials and products containing alkali-activated binders.

SUMMARY OF THE INVENTION

The combination waste binder of the present invention comprises Portland silica clinker in an amount of 5 to 40 wt%, preferably 10 to 30 wt%, 94.5 to 50 wt%. fly ash or a mixture of fly ash and metallurgical slag mixed in any ratio or metallurgical slag, and an alkaline activator in an amount of 0.5 to 10% by weight, preferably 3 to 7% by weight. The essence of the binder according to the invention consists in that the alkaline activator is waste alkaline water, leachates from red and brown sludge dump sludge as waste after treatment of the bauxite by alkaline leaching by the Bayer method of Al ₂ O ₃ and aluminum production, and with an active alkali component content of analytically expressed as 0.01 to 6.5 wt. % Na ₂ O.

The combination binder according to the invention based on waste and resp. mixtures of different wastes and by-products is based on a combination of hydraulic, geopolymer, pozzolanic and / or latent hydraulic properties activated by the addition of alkaline waters, leaches, resp. concentrated alkaline waters, leachates formed by free evaporation on large areas or in evaporators, or drying ovens, or by evaporation at low temperatures, resp. solids from alkaline waters, leaches, resp. by addition of alkaline waters, leachates neutralized with SO ₄ ² , SO 3 ² , SO 3, SO ₂ , CO ₃ ² , HCO ³ , CO ² , SiO ² , SiO ^{4 4} , SiO ^{3 2} , non-stoichiometric silicates of formula ΞίχΟγ ² without drying; dehydrated to various degrees, resp. dehydrated to dry, moisture-free inorganic salts, inorganic salt crystallohydrates as neutralization product, resp. their combination.

The combined effect of the hydraulic properties of the silicate Portland clinker, the pozzolanic properties of the ashes, in particular the silica ash, the latent hydraulic properties of the metallurgical slags, in particular the granulated blast furnace slag, and the geopolymeric properties, e.g. j. inorganic polycondensation reactions of aluminosilicate materials in an alkaline - alkaline medium to form geopolymers - inorganic alkaline aluminosilicates activated after addition of alkaline water, leachate and concentrates resulting therefrom, neutralization products.

Waste alkaline waters, leaches are formed on the sludge dumps of red and brown sludge dumps as waste after treatment of bauxite by alkaline leaching by the Bayer method from the production of Al ₂ O ₃ and aluminum Al. They are characterized by varying concentrations of the active alkaline components Na ⁺ and OH, therefore it is preferable to concentrate them to the resulting products. The resulting products are a concentrate with increased dry matter and a quantity of Na ⁺ and OH, formed by free evaporation on large areas or in evaporators or driers, or by low temperature evaporation freeze. The concentrate can be dehydrated to varying degrees in the dry matter content, resp. dehydrated to moisture-free dry matter. Waste alkaline water, leachates, their concentrate, resp. moisture-free dry matter can be neutralized by the addition of various acids H ₂ SO 4, H ₂ SP ₃ , H ₂ CO ₃ , SiO ₂ or nano-SiO ₂ silica, micro-SiO ₂ , or gaseous SO ₃ , SO ₂ and CO ₂ . This creates sulphates SO _4, SO ₃ sulphites, carbonates CO _3, HCO ₃ bicarbonate, silicate SiO _4, SiO _3, a non-stoichiometric silicate _x Si _y O ^z, with the majority-bound Na ^+. The neutralization may also be followed by concentration to dry inorganic salts, without moisture.

Advantageously, the neutralization is effected by the use of waste gaseous CO ₂ , from thermal industrial aggregates, power plants and heating plants, which helps to reduce the total CO ₂ emissions to the atmosphere. This results in Na ₂ CO ₃ .

Advantageously, the neutralization is effected by using waste H ₂ SO 4, which is available in a relatively large volume, since H ₂ SO 4 is industrially bulk produced and utilized e.g. in car batteries, pickling baths of steel sheets and the like. This results in Na ₂ SO 4.

Advantageously, the neutralization is effected by using silica drift, amorphous SiO ₂ as a by-product in the production of crystalline silicon or ferro-silicon. This results in non-stoichiometric, amorphous sodium silicates.

Due to the different concentrations of the active alkaline components Na ⁺ and OH, the starting alkaline waters, leachates and the resulting products can also be concentrated by the addition of various types of inorganic salt and inorganic alkaline crystalline hydrates based on Na ₂ SO ₄ , Na ₂ SO ₄ .10H ₂ O , Na ₂ SO ₃ , Na ₂ CO ₃ , Na ₂ CO ₃ .10H ₂ O, NaHCO ₃ , Na ₄ SiO ₄ , Na ₂ SiO ₃ and / or K ₂ SO ₄ , K ₂ SO ₃ , K ₂ CO ₃ , KHCO ₃ , K ₄ SiO ₄ , K ₂ SiO ₃ , excluding chlorides. When K ⁺ salts are used, in some cases the concentration required for alkaline activation is approximately twice as high as Na ⁺ , which also leads to a shortening of the solidification time.

Especially preferred is to use the concentration of the starting alkaline waters, waste liquor from which the resulting products of various industrial wastes, such as solutions of inorganic salts, saturated or supersaturated solution or crystalline residue after evaporation of the water containing Na ₂ SO 4, which is produced as waste from a variety of chemical production. from the production of hydrochloric acid, ascorbic acid, chromium-based chemicals, lithium carbonate LiCO ₃ , cellulose, viscose fibers, resoncinol (crystalline phenol, 1,3-benzenediol), silica-based pigments of SiO ₂ , battery recycling.

The solution thereby helps to maximize the recovery of waste in the production of the combined binder based on waste.

These waste alkaline waters, leachates and their products serve as activators of geopolymerization, the activator being added in an amount analytically expressed as 0.01 to 6.5% by weight. % Na ₂ O, preferably 1.5 to 2.5 wt. % Na ₂ O per combination binder.

Waste alkaline water, leachates, their products can serve as mixing water, make-up water, liquid activator, dry activator in cements, geopolymers of concrete, mortars, grouts, self-leveling layers, based on a combined binder.

Waste and by-products from heat or power generation, fly ash metallurgy, metallurgical debris with minimal addition of Portland silicate clinker, although conventional Portland ginkolymers do not contain Portland clinker, are further used to produce the combined binder.

The fly ash according to the solution is from the group of silica fly ash, calcium fly ash, fluid fly ash, preferably silica fly ash, which meets the requirements of STN EN 197-1, STN EN 450-1 and STN EN 206-1.

The pozzolanic activity resulting from the chemical and mineralogical composition of siliceous ashes. The pozzolanic activity consists in the reaction of active SiO ₂ and Al ₂ O ₃ with Ca (OH) ₂ portlandite present. Ashes, pozzolans, when mixed with water, do not solidify or harden themselves, but when finely ground, they react with dissolved Ca (OH) ₂ in the presence of water at normal temperature to form calcium silicates and calcium aluminates, which carry gradual strengths.

Calcium ashes are richer in active CaO, so in addition to the pozzolanic activity, hydraulic properties also increase in this case. A different situation is in the case of the fluidized fly ash produced by the fluidized bed combustion technology, which, unlike the previous fly ash, also contains free lime CaO and anhydrite

CaSO ₄ , therefore, the fluidized-bed ash solidifies and hardens undefined when mixed with water. The hydrating products of spontaneous solidification and hardening are portlandite Ca (OH) ₂ and gypsum CaSO ₄ .2H ₂ O.

In the case of the addition of an alkaline activator to the ashes, the SiO-Si, Al-O-Al and Al-O-Si bonds are disrupted in the first stage, the NASH or KASH hydrates precipitate and coagulate in the second stage and polymerization and three-dimensional structure are formed in the third wherein, after brief warming, autoclaving at up to about 85 ° C, the three-dimensional structure strengthens and subsequently crystallizes for a long time. This results in geopolymers with a three-dimensional clay with a siliceous lattice, which can be expressed by the empirical formula M _n [- (SiO ₂ ) _z -AlO ₂ ] _n. W H ₂ O, where M is an alkaline cation Na ⁺ or K ⁺ .

The metallurgical slag according to the solution is from the group of blast furnace granulated slag, blast furnace air cooled slag, steel slag, ladle slag, slag from production and refining of non-ferrous metals preferably blast furnace slag, which meets the requirements of STN EN 197-1, STN EN 15167-1 and STN EN 206-1.

The finely ground granulated blast furnace slag has latent hydraulic properties due to its chemical and phase composition and, in particular, due to its high vitreous phase content. The ability of finely ground glassy as well as crystalline slags to react with water, solidify and harden depends on their phase composition, in particular their degree of recrystallization. Completely crystallized blast furnace slags react very little with water, respectively. at all. The bonding properties of the debris can be enhanced by the addition of Portland clinker and gypsum, gypsum, resp. anhydrite, resulting in Portland slag cements, blast furnace cements and others. The addition of gypsum, anhydrite or gypsum creates slag binders or the addition of hydroxides, sulphates, carbonates, Na or K silicates to form geopolymers. The presence of ions SO ₄ ^2- generated kalciumhydrosulfoalumináty C3A.3CaSO4.32H2O ettringite, which extends the time of the monosulfate C3A.CaSO4.12H2O. The use of Na ⁺ or K ⁺ compounds to drive slag hydration produces NCSH sodium or potassium KCSH hydrosilicates, which gradually recrystallize to calcium hydrosilicates. Amorphous compounds of the zeolite type Men [- (Si-O) _z -Al-O] wH ₂ O may also be _produced at an increased alkali concentration, the formation of which is supported by an increase in the Al / Si ratio and a decrease in the Ca / Si ratio. Further hydration of the slag is already carried out by its direct reaction with water, resulting in the majority of CSH gels with reduced C / S ratio and increased Al content (CA-SH), hydration products of C ₄ AH ₁₃ , C ₂ ASH ₈ , solid hydrotalcite Mg mineral solutions ₆ Al ₂ CO ₃ (OH) ₁₆ .4H ₂ O and hydrogranates C ₃ AS ₃ .Hn, C ₆ AFS ₂ H ₈ and ettringite C ₃ A.3CaSO ₄ .32H ₂ O. The type and chemical composition of hydration products depend on the chemical and mineralogical composition of the metallurgical slag, the type of activator, the surface area and the method of treating the solidifying mixture.

Hydrating Portland silicate clinker for C ₃ S and C ₂ S produces CSH gels and Ca (OH) ₂ portlandite, for C ₃ A and C ₄ AF, calcium aluminate hydrates are formed in which part of the aluminum is replaced by CA (F) - H (this is the full range of C ₃ A (F) H ₆ , C ₂ A (F) H ₈ and C ₄ A (F) Hi ₃ hydration products). The presence of gypsum, anhydrite and gypsum are reacted, C ₃ A and C ₄ AF vysokosulfátový ettringite C ₃ A.3CaSO ₄ .32H ₂ O, passing through the nízkosulfátový monosulfate C ₃ A.CaSO ₄ .12H ₂ O CSH gel is amorphous and gradually prekryštalizovávaním mainly it consists of tobermorite 5CaO.6SiO ₂ .5H ₂ O and xonotlite 5CaO.5SiO ₂ .H ₂ O.

The addition of CaO to the combination binder of the present invention, which contains waste alkaline waters, leachates, and their products as activator modifies its resulting properties. Such a combined binder does not need to be preheated by overheating, autoclaving at up to about 85 ° C to harden it, as is the case with alkaline-activated aluminosilicates, but solidification and hardening may also occur at normal temperatures of 5 to 35 ° C. Modification of O-Α-S-H or K-A-S-H gels with CaO allows, at certain proportions, even the production of ready-mixed concrete with common properties, as is the case with Portland cements.

According to this solution, the addition of CaO to the combination binder is provided mainly by means of Portland silicate clinker added in an amount of 5 to 40% by weight, preferably 10 to 30% by weight. and minorly by means of materials such as calcium ash, fluid fly ash, metallurgical debris, replacing 94.5 to 50 wt. the amount of silica fly ash in the combination binder and, in the case of granulated blast furnace slag, this substitute for silica fly ash may be complete.

The mechanisms of reactions involving hydration of the combination binder are different. Without the addition of an activator, hydration reactions occur as a result of the presence of Portland silicate clinker, based on the formation of Ca (OH) ₂ portlandite from the hydration of C ₃ S, to form a CSH gel from the pozzolanic reaction of silica ash and activation of latent hydraulic properties of granulated blast furnace slag. The additional portlandite Ca (OH) ₂ can also be introduced into the system by the presence of calcium and fluidized fly ash and steel and ladle debris.

In the presence of Na ⁺ alkali after the addition of the activator, the pH of the liquid medium increases, helping to disrupt the dissolution of the ash and metallurgical debris structures and consequently to geopolymerization.

The mechanism of hydration reactions of the combination binder depends on the type of activator used. Alkaline waste water itself, leachates, their products increase the pH of the liquid environment. Due to the composition of the combined cement, also combined hydration reactions take place and different hydration products are formed.

In the case of neutralization of waste alkaline waters, leachates, their products with amorphous SiO2 as a by-product in the production of crystalline silicon or ferro-silicon, non-stoichiometric, amorphous sodium silicates analytically expressed as Na ₄ SiO ₄ , Na ₂ SiO ₃ compounds , which directly participate in geopolymer reactions and increase the pH of the liquid medium.

For neutralization of the waste alkaline water, liquor, the product by the waste gas of CO ₂ from flue gases from thermal industrial aggregates, power stations and heating plants produced Na ₂ CO _3, and by the waste H ₂ SO ₄ from the car battery, the pickling bath is formed Na ₂ SO _fourth Dissolution of these types of salts does not increase the pH of the liquid medium directly but indirectly by secondary reactions with the portlandite Ca (OH) ₂ (1, 2). The portlandite Ca (OH) _{2 itself} resulting from the hydration of C ₃ S increases the pH of the liquid medium to about 12.5.

Ca (OH) ₂ + Na ₂ CO ₃ -> CaCO ₃ + 2 NaOH (1)

Ca (OH) ₂ + Na ₂ SO ₄ + 2 H ₂ O - + CaSO ₄ .2H ₂ O + 2 NaOH (2)

On contact of Na ₂ CO ₃ and Na ₂ SO ₄ with Ca (OH) ₂ portlandite, reactions (1, 2) generate NaOH, which efficiently increases the pH of the liquid medium and aids geopolymerization. In the case of Na ₂ CO ₃ , practically inactive CaCO ₃ calcite is produced, and in the case of Na ₂ SO ₄ , gypsum CaSO ₄ .2H ₂ O is formed, which reacts with C ₃ A from Portland clinker to react to ettringite C ₃ A.3CaSO ₄ .32H ₂ O according to reaction (3).

C ₃ A + 3 CaSO ₄ .2H ₂ O + 26 H ₂ OC ₃ A.3CaSO ₄ .32H ₂ O (3)

The resulting ettringite increases the volume of solid reaction products by up to four times, increasing the density and initial strength of cement pastes.

These hydration processes result in two types of gels in the cement paste of the combination binder, namely a CSH gel with an increased content of aluminum Al in the structure C- (A) -SH) from hydration of clinker and granulated blast furnace slag and NASH gel with an increased calcium content. C) -NASH from the alkaline activation of fly ash. Together, these gels form a mixture expressed as a (N, C) -A-S-H gel and are responsible for the development of strengths.

The presence of fly ash and granulated blast furnace slag improves some properties of the combination binder compared to Portland cement.

The fly ash in the mixed binder acts as a solid plasticizer when mixed on the concrete mixture, improves the workability of fresh concrete, pumpability of liquid concrete, it is advantageous in concrete where there is usually a lack of fine particles - particles up to 0.25 mm. mixing water, prevents segregation of very liquid concretes, prevents mixing of concrete during concreting, enables easier processing, laying of concrete, contributes to sealing of concrete structure, which is suitable for water-concreting concretes, increases resistance of concrete against some influences of chemically aggressive environment provides prevention of alkali-silica reaction, contributes to reduction of hydration heat, which is beneficial especially in the realization of massive constructions, enables to extend the workability time of fresh concrete, which is advantageous during transport concrete.

The granulated blast furnace slag in the combined binder when mixed with a concrete mix increases long-term compressive and tensile bending strengths compared to pure cement, reduces hydration heat, improves processability and stability of the mix, reduces permeability by creating a compact cement stone structure, increases resistance to sulphate and aggressive water, against chemical corrosion, against chlorides, ensures prevention of the alkali-silica reaction. For concrete, it is advantageous to extend the setting time of the concrete and to optimize the grain size curve of the aggregate as a filler.

Thus the combined binder is characterized by lower development of hydration heat, lower development of strength, low shrinkage, higher chemical resistance, resistance to sulphates, chloride, aggressive water and solutions, ensures prevention of alkali-silica reaction, slows down the process of carbonation of concrete surfaces. , transportability, stability of fresh concrete. Although the combined binder reduces the initial strengths, it increases the long-term compressive and flexural strengths compared to pure Portland cement.

The application of the combined binder in concrete ensures that the required consistency of fresh concrete is achieved with a lower water coefficient than in the case of application of cements for common use according to STN EN 197-1. The setting time of the concrete is prolonged, which is advantageous for concrete.

Hydration products by creating a compact structure of cement stone reduce its permeability, seal the pore system of the cement matrix, which leads to increased waterproofness of the concrete, increasing the density of the cement putty, and also increases the chemical resistance of the concrete.

Hydrating geopolymer products in the form of (N, C) -ASH gel are much more heat and open flame resistant than conventional concrete consisting of CSH phases and Ca (OH) ₂ portlandite.

The combined binder does not impair the frost resistance of the concrete. However, in the case of excessive dosing of the mixed water in the concrete with the combined binder, the rheology of the fresh concrete changes and there is a breakdown - water separation on the surface of the deposited concrete, which reduces the resistance of the concrete to pressurized water, deicing agents and freeze cycles.

The combination binder is suitable for the production of ready-mixed concrete, and without the use of chemical additives such as plasticizers and superplasticizers, concrete of lower strength classes C 8/10 to C 20/25 according to STN EN 206-1 and using plasticizers or superplasticizers can be made from them higher classes of concrete up to C30 / 37.

The combination binder is an ideal starting component for the production of various cement-containing mixtures, such as low hydration heat concretes, low initial strength cements, increased chemical resistance concretes, concrete mixes, concrete mixes for the production of blocks and prefabricates for non-load-bearing structures, concrete mixes for subfloors of pavements, large concrete areas, airports, various halls, tunnels, bridges, viaducts, cement containing mixtures for stabilizing substrates, cement-reinforced aggregates, concretes for massive and large-scale construction, masonry mortars, plastering mortars, dry plaster mixtures, grouting mixtures, sealing suspensions, remediation mixtures and the like, which will be exposed to chemically aggressive environment, high temperatures, open flame.

Combined binder is suitable for production of non-structural prefabricates, concrete products such as interlocking pavers, curbs, for production of sewer pipes and elements, for concrete elements for chemically and biologically aggressive environment, septic tanks, sewage treatment plants, floors in animal products, rendering plants, chemical products , biotechnology, food, and fire resistant concrete elements.

Advantageously, the combined binder based on waste and by-products is a low CO2 binder. It contains only 20% of classic Portland clinker, saving up to 80% CO2 emissions compared to conventional Portland cement. The combined binder can even be produced using CO ₂ from the flue gas from Portland clinker firing, respectively. CO ₂ from waste gases from other thermal and industrial combustion units.

All of the given wastes and by-products are advantageously recovered in material. The combined binder allows maximum utilization of various wastes and by-products in its production.

It is very advantageous that the combined binder based on wastes and by-products is always produced at a lower cost than conventional Portland cement.

It is also advantageous that the combination binder mixture without the addition of an alkaline activator can be used for dealkalization of wet red and brown sludge, for strengthening landfills, heaps, deposits, sludge field dams, red and brown sludge tailings, for implementing various security and anti-seepage layers and barriers to thicken liquid red and brown sludge and alkaline waters. The alkaline activator in this case is a high content of Na ⁺ and OH in sludge and sludge alkaline waters. The mixture in these cases can serve for prevention, remediation and also as a solution to ecological disasters.

It is also advantageous that the continuous collection and utilization of the alkaline waste water according to the solution would reduce the alkalinity of the red and brown sludge deposits after a certain long-term re-infiltration of the waste water and could be used and disposed of in bulk after an acceptable decrease of Na ⁺ concentration. cement plants in the production of cement clinker as an important raw material component using alternative fuels with higher chlorine content (STN EN 15359) and by-pass operation.

The production of a combined binder based on waste is also feasible on existing, available equipment commonly used in the cement industry.

The production of the combined binder is carried out by simply mixing, crushing, grinding waste and by-products with waste alkaline waters, leachates, or their concentrate formed in evaporators, dryers or dry matter, salts that appear to be neutralized with alkaline water, to form the combined binder.

Mixing can be carried out in various types of mixing units (mixing cores, mixers, mixers, homogenizers, mixers, for the production of cements, geopolymers, building binders, dry plaster mixtures, concrete, mortars, etc.), crushing can be carried out in crushing units, the mixing may be carried out in the milling process in the milling aggregates with the arrangement of spherical grinding cartridges and / or grinding bars and / or the grinding rollers, and / or in the sorting aggregates in the sorting process.

Waste alkaline waters can also be fed to mills when grinding the combined without pre-added activator. Here, the dehydration of the alkaline waters occurs by heat drying resulting from the milling process or in the case of external supply of various flue gases (eg waste gases from the furnace system, flue gases from the auxiliary burners of combustion chambers, etc.).

DETAILED DESCRIPTION OF THE INVENTION

Example 1

For the preparation of alkaline activators waste alkaline waters from red and brown sludge sludge were used. The chemical composition of the alkaline waste water before concentration (normal) and after concentration (concentrate) in the evaporator is given in Table no. The concentrate was subjected to neutralization with waste sulfuric acid H ₂ SO ₄ from car batteries and subsequently subjected to electrodialysis, which by electrophysical processes ensured the separation of the inlet stream into a low salt diluate which can be discharged into the sewer and a high sodium sulfate concentrate. This was subsequently processed to a final product which was anhydrous sodium sulfate with a purity of 97% Na ₂ SO ₄ on a crystallization evaporator. In the process of neutralization was carried out at the same time reducing the toxicity of ^6-yl powerful of Cr-toxic to 3-valent chromium Cr ^AD, while the water is removed from the present heavy metals and aluminum. These fell out of the process in the form of sludge, which is then disposed of in the landfill.

Table no. 1 Chemical composition of alkaline waste water before concentration (normal) and after concentration (concentrate) in the evaporator, which was the starting component for the preparation of alkaline activators for geopolymer cements_

Labeling-unit normal concentrate CN- tot. [Mg / 1] 0,054 0,076 Cl [Mg / 1] 41.5 260 F- [Mg / 1] <1 <5 (SO4) 2 [Mg / 1] 4072 24098 S 2- [Mg / 1] <0.01 <0.01 (NO3) - [Mg / 1] 18.0 64.0 (NO2) - [Mg / 1] 0.17 <0.01 (HCO3) - [Mg / 1] <0.3 <0.3 (NH 4) + [Mg / 1] 1.47 1.96 The [Mg / 1] 156 710 On the [Mg / 1] 11820 53990 CD [Pg / i] <3 <3 ba [Mg / 1] 0.03 0.04 and [Pg / i] 7250 25750 Cr tot. [Pg / i] 49390 5549 Cr6 + [Pg / i] 49390 620 Cu [Pg / i] 65 161 Ni [Ug / l] <20 44 Pb [Ug / l] <50 <50 sb [Ug / l] 18 270 with [Ug / l] 83 330 Te [Mg / 1] <1 <1 IN [Pg / i] 2440 11110 Zn [Pg / i] 86 245 hg [Pg / i] 0.3 1.0 Be [Pg / i] <1 <1 sn [Mg / 1] <0.3 <0.3 when [Mg / 1] <0.1 <0.1 What [Pg / i] <20 <20 Mn [Mg / 1] 0.07 0.30 Mo [Pg / i] 6928 31440 TI [Mg / 1] <0.5 <0.5 PH 13.0 13.2 br [Mg / 1] 0.5 2.5 ca [Mg / 1] 6.9 12.5 P [Mg / 1] 4.56 0.86 Al [Mg / 1] 538 2143 fe [Mg / 1] 0.64 26.0 Are you [Mg / 1] 59.8 189 you [Mg / 1] <0.1 0.24 mg [Mg / 1] 1.9 4.4

Similarly, 95% Na ₂ CO ₃ was prepared, but for neutralization, the concentrate was fed to a special pilot facility that allowed multiple passage of waste flue gases from a high CO ₂ cement kiln rotary kiln from burned fuels and decarbonisation of natural carbonates through the concentrate layers from alkaline waste water. Prepared Na ₂ SO ₄ and Na ₂ CO ₃ were used as alkaline activators for combined binders - geopolymer cements.

Example 2

The alkaline activators Na ₂ SO ₄ and Na ₂ CO ₃ prepared by the procedures described in Example 1 were used in the form of free-flowing salts in the production of combination binders - geopolymer cements. Various input wastes and by-products, including Portland silica clinker, whose chemical composition is given in Table 2, have been used to produce geopolymer cements. 2

Table no. 2 Chemical composition of input components for geopolymer cement

weight. % clinker VGT KP FP CaO 66.13 39,24 3.36 25.78 SiO ₂ 21.69 40.13 51.42 33,25 A1 ₂ O ₃ 5.31 7.19 26.93 18.65 Fe ₂ O ₃ 2.83 0.27 7.27 5.84 MgO 1.44 10.04 2.10 1.34 Na ₂ O 0.04 0.31 0.17 1.01 K ₂ O 1.00 0.52 3.28 0.98 SO ₃ 0.53 1.50 0.87 11,30 Str. from. 0.85 1.10 1.84 1.20

VGT - blast furnace granulated slag, KP - siliceous fly ash, FP - fluid fly ash

Composition of combined binders - geopolymer cements no. 1-3 were modified in the sequence shown below.

Composition of geopolymer no. 1:

Clinker 20%

Silica fly ash 75%

Na ₂ SO ₄ 5%

Composition of geopolymer no. 2: Clinker 18%

Silica fly ash 73%

Fluid fly ash 5%

Na ₂ CO ₃ 5%

Composition of geopolymer no. 3: Clinker 15%

Slag VGT 10%

Popolček 71%

Na ₂ SO ₄ 4%

The geopolymers were ground in conventional cement spheres to a surface area of about 400 m ² / kg. The standard samples for the determination of strengths were prepared from geopolymers, which are shown in Table 2. 3 and solidification times and normalized density are shown in Table 3. 4th

Table no. 3 Strengths of geopolymers determined according to STN EN 196-1.

MPa PT / PO 1 PT / PO 2 PT / PO 7 PT / PO 28 PT / PO 90 GPC. 1 15.3 / 3.1 20.3 / 4.1 36.8 / 7.8 53.8 / 9.6 61.2 / 9.7 GPC. 2 12.1 / 2.7 16.7 / 3.4 32.7 / 6.8 48.1 / 8.6 56.7 / 9.1 GPC. 3 13.4 / 2.9 17.4 / 3.5 35.6 / 7.6 52.1 / 8.9 59.5 / 9.4

GP - geopolymer, PT - compressive strength, PO - flexural strength, numbers 1, 2, 7, 28 and 90 are days

Table no. 4 Solidification times, standardized density and volume stability of geopolymers determined according to STN EN 196-3.

geopolymer ZT min. KT min. NH% OS mm GPC. 1 255 305 32.6 2.5 GPC. 2 225 265 30.0 5.7 GPC. 3 215 255 29.8 3.6

ZT - start of solidification, KT - end of solidification, NH - normalized density, OS - volume stability

In the fire resistance tests, geopolymer binders have been shown to be resistant to temperatures up to 200 ° C. In chemical resistance tests, it has been shown that geopolymer binders meet the highest degree of aggressiveness of the chemical action of XA3 waters - a strongly aggressive environment according to STN EN 206-1: 2002 and STN EN 2061 / NA: 2009 (Table 5).

Table no. 5 Chemical limit values for individual degrees of water aggressiveness according to STN EN 206-1: 2002 and STN EN 206-1 / NA: 2009

Chemical characteristics XA1 XA2 XA3 SO ₄ ² mg / L > 200 and <600 > 600 and <3000 > 3,000 and <6,000 PH <6.5 and> 5.5 <5.5 and> 4.5 <4.5 and> 4.0 CO ₂ mg / liter aggressive > 15 and <40 > 40 and <100 > 100 until saturation NH ₄ ⁺ mg / liter > 15 and <30 > 30 and <60 > 60 and <100 Mg ²⁺ mg / L > 300 and <1000 > 1,000 and <3,000 > 3000 to saturation

The geopolymer hydration heat development tests did not exceed 185 J / g after 7 days of hydration according to STN EN 196-8, therefore, geopolymers comply with low hydration heat cements according to STN EN 197-1 / A1 as they met the condition that the hydration heat determined according to STN EN 196-8 shall not exceed 270 J / g in 7 days when determined according to STN EN 196-9 after 41 hours and also comply with cements with very low hydration heat in accordance with STN EN 14216, as they have met the condition that hydration heat STN EN 196-8 shall not exceed 220 J / g in 7 days when determined according to STN EN 196-9 after 41 hours.

Due to the low content of Portland silica clinker in the resulting geopolymers, CO ₂ emissions could be saved at 80-85%.

Example 3

Combination binders - geopolymer cements - prepared according to the procedures given in Example 2 were used for the preparation of geopolymer concrete of lower strength classes C 8/10 to C 20/25 according to STN EN 206-1 without the use of plasticizers.

Table no. 6 Chemical composition of input components for geopolymer concrete

weight. % VCHT DOT VAP CuT CaO 41,73 52.30 58.97 7.48 SiO ₂ 40.57 12.81 13.97 27.26 A1 ₂ O ₃ 8.12 1.64 17.77 7.01 Fe ₂ O ₃ 2.81 29.78 1.90 46,64 MgO 8.44 2.54 3.30 1.90 K ₂ O 0.72 0.04 0.06 0.40 Na ₂ O 0.19 0.07 0.07 1.07 SO ₃ 2.39 28 1.98 0.15 Str. žíh. 0.09 6.02 5.32 + 4,30

Metallurgical slag VCHT - blast furnace air cooled slag, DOT - demetallised steel slag, VAP - lime ladle slag, CuT - slag from copper refining.

Table no. 7 Composition of fresh concrete mixtures made of geopolymer cements to achieve consistency S3 according to cone setting according to STN EN 206-1: 2002

kg GP KAV Aggregates 0-4 mm Aggregates 4-8 mm Aggregates 8-16 mm Filer up to 0.25 mm C 8/10 270 185 762 362 781 - C 12/15 300 190 687 372 781 70 C 16/20 360 190 627 376 788 - C 20/25 390 190 592 361 773 70

GP - geopolymer cement, KAV - waste water alkaline water concentrate

For geopolymer concrete geopolymer no. 2 for class C 8/10, geopolymer no. 3 for class C 12/15, geopolymer no. 1 for classes C 16/20 and C 20/25, and as a mixing water, an alkaline waste water concentrate was used.

Blast furnace air-cooled slag in fractions 0-4 mm, 4-8 mm, 8-16 mm was used as artificial compacted aggregate and finely ground calcium pelvic slag with max. up to 0,25 mm grain size for class C 12/15 with geopolymer no. 3 and for class C 20/25 with geopolymer no. First

Demetallised steel mill slag in 0-4 mm, 4-8 mm fractions was used as artificial dense aggregate and an 8-16 mm fraction was prepared from copper refining slag for class C 8/10 with geopolymer no. 2 and for class C 16/20 with geopolymer no. First

Table no. 8 Cube strength achieved f _ck . _{cube of} hardened concrete after 2, 7 and 28 days according to STN EN 12390-3

9 f - * - ck.cube 7 f '- * - ck.cube 28 f _c k.cube C 8/10 4.8 10.4 16.0 C 12/15 5.7 11.4 18.7 C 16/20 6.9 14.6 22.2 C 20/25 8.0 16.8 25.0

Fresh concrete mixtures made of geopolymer cements are suitable for the preparation of ready-mixed concrete for concrete classes C 8/10 to C 20/25 with S3 consistency according to the cone setting without the use of plasticizers.

Example 4

Combined binder - geopolymer cement no. 4 with the addition of a silica drift and an alkaline activator in the form of dry matter from the alkaline waste concentrate given in Example 1 was used for surface consolidation and remediation of cracks in the dikes of wet red and brown sludge sludge. The composition of fresh remediation mortar is given in table no. 9. The dry matter from the alkaline waste concentrate of Example 1 was obtained by drying in an oven using the flue gas from a cement rotary kiln. The additional alkaline activator in this case was also a high content of Na ⁺ and OH in the sludge and separated surface sludge alkaline waters.

Composition of geopolymer no. 4:

Clinker 15%

Slag VGT 10%

Popolček 70%

Silica drift 3%

KAV dry matter 2%

Table no. 9 Composition of fresh redevelopment mortar for reinforcing the dykes of wet red and brown sludge.

kg GP KAV Sand 0-2 mm C 8/10 360 205 1690

GP - geopolymer cement, AV - alkaline water waste concentrate

These examples are illustrative only and do not exhaust all variants of the present invention within the scope of the invention.

Industrial usability

Combination binder based on mixtures of different wastes and by-products is characterized by low CO ₂ emission, lower development of initial strengths and higher development of long-term compressive and tensile bending strengths, lower development of hydration heat, higher chemical resistance, resistance to sulphates, chlorides, carbonation , by preventing the alkaline-silica reaction of the aggregate, with higher fire resistance. It is designed for the production of concrete, mortars for plastering and masonry, grouting mortars, dry plaster mixtures and the like. It is suitable for massive constructions of large-volume and large-scale concretes, foundations of buildings, for subfloors of pavements, substrates of cement stabilized aggregates, landfills, for preparation of concretes of lower grades C 8/10 - C 30/37, for concretes for non-structural purposes non-load-bearing layers, prefabricated elements, decorative concrete elements, for concretes against aggressive water, soil, for production of blocks exposed to adverse climatic conditions, has increased resistance to chemical and biological corrosive influences, for sewer pipes, fittings, septic tanks, sewage treatment plants production, rendering plants, chemical production, biotechnology, food industry. Ensures the required consistency of fresh concrete at a lower water coefficient than in the case of normal use cements according to STN EN 197-1, acts as a rigid plasticizer in fresh concrete, increases setting time, increases cementitiousness, improves workability and stability fresh concrete mixtures. Alkaline wastewater from landfill sites and red and brown sludge sludge from bauxite processing and various wastes and by-products in the form of ash and metallurgical debris are used for its production.

PATENT CLAIMS

Claims (5)

A waste-based combination binder comprising Portland silica clinker in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, 94.5 to 50% by weight. fly ash or mixtures of fly ash and metallurgical slag mixed in any ratio or metallurgical slag, and an alkaline activator in an amount of 0.5 to 10% by weight, preferably 3 to 7% by weight, characterized in that the alkaline activator is waste alkaline water, leachates from the tailings ponds of red and brown sludge as waste from the treatment of bauxite by alkaline leaching in the production of Al ₂ O ₃ , and the resulting products in an amount containing an active alkali component of analytically expressed as 0.01 to 6.5% by weight; % Na ₂ O. Waste-based combination binder according to claim 1, characterized in that the products formed from the alkaline water and / or the leachate are thickened concentrates with a high content of Na ⁺ and OH and / or dry matter, and / or alkaline water neutralization salts and and / or mixtures of said salts with alkaline waters, leachates, concentrate, dry matter. 3. Combination binder based waste of claim 2, characterized in that the neutralization of the alkali salt of the water and / or the extracts, concentrate, dry matter content of the sulfate SO ₄ ^2, SO 3 ² sulfites, carbonate CO 3 ^2, HCO 3 bicarbonates, silicates, SiO 4 ^4, SiO3 ² , non-stoichiometric silicates Si _x O _Y ^z , with a majority of Na ⁺ bound. Waste-based combination binder according to claim 2 or 3, characterized in that the alkaline waters and / or leachates and / or the concentrate comprise an addition of H ₂ SO ₄ , H ₂ SO ₃ , H ₂ CO ₃ , and / or nano-SiO ₂ , micro-SiO ₂ , silica SiO ₂ , and / or SO ₃ , SO ₂ and CO ₂ gas. Waste-based combination binder according to claim 2, 3 or 4, characterized in that the alkaline waters and / or leachates and / or the concentrate and the resulting products contain an addition of waste of inorganic salts based on Na ₂ SO ₄ , Na ₂ SO ₄ .10H ₂ O, Na ₂ SO ₃ , Na ₂ CO ₃ , Na ₂ CO ₃ .10H ₂ O, NaHCO ₃ , Na ₄ SO ₄ , Na ₂ SiO ₃ and / or K ₂ SO ₄ , K ₂ SO ₃ , K ₂ CO ₃ , KHCO ₃ , 10 SiCl ₃ , K ₂ SiO ₃ . End of document