KR100448343B1 - Admixture for concrete comprising molasses fermentation by-product - Google Patents

Abstract

The present invention relates to a concrete admixture comprising molasses fermentation by-products produced in molasses fermentation processes. The concrete admixture containing the molasses fermentation by-product shows an equivalent performance or more in comparison with the existing expensive lignin-based admixture in terms of physical properties, thereby reducing the production cost when preparing the admixture. In addition, when molasses fermentation by-products, which are by-products generated during the molasses fermentation process, are added to concrete, a large amount of by-products can be efficiently recycled, thereby reducing the environmental pollution that may be caused by ocean dumping of the fermentation by-products. There is this.

Description

Admixture for concrete comprising molasses fermentation by-product}

The present invention relates to a concrete admixture, and more particularly, to an admixture for concrete comprising an organic by-product produced during the molasses fermentation process.

Concrete is the foundation of modern construction and civil engineering, and the strength of concrete depends on how homogeneously the added materials and components are mixed. In this respect, it is essential to develop new admixtures that are superior in the use and performance of admixtures to maximize the homogeneous state of the materials and components used in the manufacture of concrete. As safety accidents increase due to the recent increase in large-scale safety accidents, high strength and high quality of concrete are required as the size of buildings increases, and the amount of admixtures in the manufacture of concrete increases steadily every year. In-house technology development is actively underway.

Admixtures provide many functionalities to concrete, and are used for the purpose of improving the properties of hardened concrete and hardened concrete by physical and chemical effects, and increasing economic efficiency. These admixtures are generally classified according to their effects and uses when using admixtures. Depending on the effect of air volume, unit quantity, condensation, and initial cure rate of concrete, AE (air entraining agent), water reducing agent, AE It is divided into air entraining and water reducing agent, high performance water reducing agent, fluidizing agent, super-delaying agent, admixture for underwater concrete, anti-rusting agent, shrinkage reducing agent, heat of hydration inhibitor, expansion agent and anti-fogging cold-proof agent.

In particular, sensitizers are classified into lignin sulfonates, oxycarboxates, alkylarylsulfonates, melamine sulfonates, polycarbonates, polyol derivatives and the like. Among them, lignin sulfonate, which is a natural polymer electrolyte, is the most commonly used admixture and has the characteristic of dissociating into lignin sulfonic anion and calcium cation in water. The anion part is adsorbed on the surface of the cement particles to form a charging layer, and by the electrostatic mutual repulsion of the charging layer, the cement particles are dispersed to prevent reagglomeration, and the flow of concrete is released by releasing water and air bubbles. Is increased.

On the other hand, molasses fermentation by-products are substances separated from fermentation broth obtained through a fermentation process using microorganisms as raw materials, and contain a large amount of various organic substances and trace elements necessary for the growth of organisms such as sugars, organics, cells, proteins and amino acids. Attention has been focused on the value of feed. However, the material is not only difficult to transport, store and handle due to its high density and viscosity, but also has difficulty in feeding, and even when added to the blended feed as a concentrate, the amount of molasses fermentation by-products does not exceed a certain ratio. Its use has been limited.

In addition, recently, it is known that molasses fermentation by-products can be used as fermentation accelerators in the production of compost, but the amount of use is increasing. However, the molasses fermentation by-product content does not exceed 20%. Some molasses fermentation by-products are currently being disposed of by dumping at sea due to the fact that the amount is not high.

However, ocean dumping, a method of treating liquid molasses fermentation by-products such as this, not only pollutes the sea, but also has a huge loss in processing costs, which is a significant loss to the corporate and national economies. As it is in danger of being discontinued, it is urgently required to establish an efficient treatment method for molasses fermentation by-products.

The inventors of the present invention while studying the way to efficiently process the molasses fermentation by-products, when using the molasses fermentation by-products as the admixture for concrete, not only can reduce the environmental pollution by marine disposal of molasses fermentation by-products, The present invention has been completed by confirming the fact that the addition exhibits good water and fluidization properties.

Therefore, the technical problem to be achieved by the present invention is to provide a concrete admixture that can exhibit excellent physical properties equivalent to or better than the lignin-based concrete admixture commonly used when applied to concrete by actively utilizing molasses fermentation by-products that are organic by-products.

In order to achieve the above object, the present invention provides a admixture for concrete containing molasses fermentation by-products.

Hereinafter, the present invention will be described in detail.

In the present invention, molasses fermentation by-products are amino acids from molasses which is a carbon source using microorganisms; Alcohol; Organic acids including citric acid; Bioactive substances including vitamins; Antibiotics; It may be obtained after performing the fermentation process to produce an enzyme or a polymer material, after removing the desired product from the resulting fermentation broth, preferably an amino acid fermentation by-product, more preferably glutamic acid or lysine fermentation by-product.

Looking at the production process of molasses fermentation by-products through the example of amino acid fermentation, first, calcium is removed from molasses using sulfuric acid before the molasses is introduced into the fermentor. Thereafter, fermentation is performed by microorganisms, and sulfuric acid is added to stop the fermentation reaction, and then microbial cells are removed by centrifugation or the like. After the microbial cells are separated, a target amino acid such as glutamic acid or lysine is separated from the remaining fermentation broth using ion exchange resins commonly used in the art. Thereafter, the remaining by-products contain various organic and trace elements such as sugars, amino acids, and proteins remaining in the fermentation, and are referred to as molasses fermentation by-products.

The molasses fermentation by-products are preferably organic salts are removed, the remaining amount of organic salts are neutralized with an alkaline solution, it is preferably included in the admixture for concrete. That is, since the initial molasses fermentation by-product has organic salts and reacts with Ca (OH) ₂ when it reacts with cement, it is preferable to remove such organic salts. The organic salts can be removed by the electrolysis method, and the alkaline solution used to remove the residual organic salts is NaOH solution, KOH solution, Ca (OH) ₂ solution, CaO solution, Mg (OH) ₂ solution and It is preferably used selected from the group consisting of MgO solution, but is not limited thereto. In addition, the neutralized solution is preferably aged for 2-5 hours at a temperature of 60-90 ℃, but is not limited thereto.

Meanwhile, the molasses fermentation by-products prepared as described above may be used alone as admixtures, but may be used in admixture with AE agents, water reducing agents, or mixtures thereof which are admixtures used for specific purposes. That is, the admixture according to the present invention may be used as a function of a water reducing agent, an AE water reducing agent, a high performance water reducing agent, a fluidizing agent, and an admixture for underwater concrete, depending on the type of other admixture mixed with molasses fermentation by-products.

AE agents which can be mixed in the admixture with molasses fermentation by-products include polyoxymethylene alkyl ether sulfates, polyoxymethylene alkylaryl ethers, sulfate derivatives of polyoxymethylene alkylaryl ethers, and lean acid esters of polyoxymethylene alkylaryl ethers. Derivatives, alkylarylsulfonates or alkylbenzolsulfonates, but is not limited thereto.

In addition, sensitizers that can be mixed in the admixture with molasses fermentation by-products include lignin sulfonates and derivatives thereof, oxycarboxates, polyol derivatives, polyoxyethylene alkylarylether derivatives, alkylarylsulfonates, formalin condensates of melamine sulfonates, It may be a formalin condensate, a polyamine condensate, or a polycarboxylic acid-based high molecular compound of naphthalene sulfonate, but is not limited thereto.

Meanwhile, to the admixture for concrete according to the present invention, a higher fatty alcohol-based dispersant may be further added together with the AE agent, a water reducing agent, or a mixture thereof.

In addition, the admixture for concrete according to the present invention may be prepared by mixing with an acrylic water-soluble polymer, metal celluloid, ethyl celluloid or a mixture thereof.

Concrete admixture containing molasses fermentation by-product according to the present invention contains a large amount of the carboxyl group and the amine group, which is a hydrophilic group, and generates an electrical mutual repulsion force between particles having a similar potential of the charging layer between the cement. Accordingly, since the cement particles are evenly dispersed, the flowability of the cement is greatly increased, and thus, the flowability of the concrete is improved.

The amount of molasses fermentation by-product added to the admixture according to the present invention may be added in an appropriate amount in consideration of economic aspects. That is, it may be added in a small amount to the existing expensive AE agent, water reducing agent or a mixture thereof, but in order to reduce the production cost is preferably added in the following mixing ratio.

Specifically, the admixture according to the present invention may be prepared as an AE reducing agent including 80-90% by weight of molasses fermentation by-product, 9-19.5% by weight of sulfonate-based compound, and 0.5-1% by weight of alkylbenzolsulfonate-based AE, but is not limited thereto. It is not. In addition, the admixtures of the present invention is molasses fermentation by-product to 80-85 wt%, water-soluble acrylic polymer 10 - Preparation fluidizing agent, including 17% by weight, metal celluloid 1-4% by weight and an alkyl sulfonic acid salt-based benzoyl AE agent 0.5-1% by weight It may be, but is not limited thereto.

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.

<Manufacture example 1>

500 g of lysine molasses fermentation by-product was placed in a reactor and then stirred at 180 rpm at a temperature of 80 ° C. While stirring, 200 g of a KOH (1000 g of water + 1000 g of KOH) solution was added dropwise over 3 minutes, and aged for 5 hours, and then cooled to room temperature to prepare a admixture for concrete.

<Manufacture example 2>

80% by weight of lysine molasses fermentation by-product of Preparation Example 1, 18.5% by weight of lignin sulfonate (Sukhyunsa, China), 1% by weight of alkylbenzol sulfonate-based AE agent (Aekyung Chemical), 0.5% by weight of higher fatty alcohol dispersant (Aekyung Chemical) After mixing the%, it was reacted for 2 hours at 60 ℃ to prepare an AE reducing agent composition for concrete.

<Manufacture example 3>

80% by weight of lysine molasses fermentation by-product of Preparation Example 1, 19% by weight of delayed-type naphthalene sulfonate formalin (curative chemistry) and 1% by weight of alkylbenzolsulfonate-based AE agent (Aekyung Chemical) were mixed, and then 60 ° C. for 2 hours Reaction to prepare a concrete AE reducing agent composition.

<Manufacture example 4>

After mixing 90% by weight of lysine molasses fermentation by-product of Preparation Example 1, 9% by weight of delayed melamine sulfonate formalin (perstorp SA, France) and 1% by weight of alkylbenzolsulfonate-based AE (Aekyung Chemical), 60 ℃ Reaction was carried out for 2 hours at to prepare an AE reducing agent composition for concrete.

Production Example 5

80% by weight of lysine molasses fermentation by-product, 17% by weight of acrylic water-soluble polymer (LG Chem), and 3% by weight of metal celluloid (Samsung Chem) were mixed and then reacted at 60 ° C. for 2 hours to prepare a fluidizing agent composition for concrete.

Comparative Example 1

98.5% by weight of lignin sulfonate (Sukhyunsa, China), 1% by weight of alkylbenzol sulfonate-based AE agent (Aekyung Chemical), 0.5% by weight of higher fatty alcohol dispersant (Samsung Chemical), followed by 2 hours at 60 ° C. Reaction to prepare a concrete AE reducing agent composition.

Comparative Example 2

99% by weight of naphthalene sulfonate formalin (curative chemical) and 1% by weight of alkylbenzolsulfonate-based AE agent (Aekyung Chemical) were mixed and reacted at 60 ° C. for 2 hours to prepare an AE water reducing agent composition for concrete.

<Example 1>

Preparation of concrete and comparison of properties

After mixing 320 kg of cement, 176 kg of water, 1003 kg of coarse aggregate, and 746 kg of fine aggregate, 0.5% by weight of cement (1.6 kg) was added to each concrete admixture prepared in Preparation Examples 1 to 5 and Comparative Examples 1 or 2. Concrete was prepared by mixing, and the physical properties of the concrete thus prepared were compared in accordance with KS F 2560 and described in Table 1 below.

Type Quality Item standard Admixture Class Comparative Example 1 Comparative Example 2 Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 % Reduction ^* over 10 12 17 15 16 17 16 17 % Of bleeding amount 70 or less 65 65 64 64 65 65 66 Difference in setting time (minutes) First -60-+90 +10 -20 -40 -30 -20 -40 -40 closing -60-+90 +30 +20 +60 +70 +60 +70 +50 Ratio of compressive strength (%) Jaeryong ^** 3 days 115 and above 120 132 131 131 132 130 132 7 days of age 110 and above 118 133 131 135 134 132 137 28 days of age 110 and above 119 135 133 133 134 131 136 Length change ratio (%) 120 or less 105 102 104 104 104 104 103 Resistance to freeze-thawing (relative dynamic modulus,%) 80 or more 94 96 96 95 95 94 95

* Susceptibility rate: It means the decrease value calculated by water / cement x 100.

** Age: The standing period after filling the formwork with concrete mixture.

As shown in Table 1, in the case of the susceptibility, it was found that the concrete to which the molasses fermentation by-product admixture of the present invention prepared in Preparation Examples 1 to 5 was higher than the concrete to which the conventional lignin-based admixture prepared in Comparative Example 1 was added. It can be, and shows almost the same performance as the concrete to which the existing naphthalene-based admixture prepared in Comparative Example 2.

In addition, the amount of bleeding was about 65% of the concrete to which the molasses fermentation byproduct admixture according to the present invention was added, and the numerical value was lower than that of the concrete without the admixture. In other words, when using the admixture according to the present invention it was confirmed that it is possible to reduce the adverse effect due to the bleeding that is often generated during concrete production because the material separation does not occur well.

On the other hand, as a result of comparing the difference in the setting time of the concrete, it can be seen that the concrete to which the admixture according to the present invention is hydrated later than the concrete to which the admixture prepared in Comparative Examples 1 and 2 is added. That is, it was confirmed that the crystallinity of the concrete is delayed when adding the admixture according to the present invention.

Looking at the ratio of the compressive strength of the concrete, it can be seen that the compressive strength of the concrete with the admixture according to the present invention was increased by about 10-16% compared to the compressive strength of the concrete with the admixture prepared in Comparative Example 1.

In addition, the results of testing the resistance to changes in length and freeze-thawing showed that the concrete exhibited the same or better performance than that of the conventional admixture.

Concrete admixture containing molasses fermentation by-product according to the present invention has a performance equivalent to that of conventional expensive lignin-based admixtures in terms of physical properties, it is possible to obtain a production cost reduction effect in economic aspects. In addition, when molasses fermentation by-products generated in the fermentation process are added to concrete, since a large amount of by-products can be efficiently recycled, there is an advantage of reducing environmental pollution that may be generated by ocean dumping of the fermentation by-products.

Claims (9)

Concrete admixture containing molasses fermentation by-product. The admixture for concrete according to claim 1, wherein the molasses fermentation by-product is glutamic acid or lysine fermentation by-product. The admixture for concrete according to claim 1, further comprising an AE agent, a water reducing agent or a mixture thereof. 4. The AE agent according to claim 3, wherein the AE agent is a polyoxymethylene alkyl ether sulfate, a polyoxymethylene alkylaryl ether, a sulfate derivative of polyoxymethylene alkylaryl ether, a phosphate derivative of polyoxymethylene alkylaryl ether, and an alkylaryl sulfonate. And alkylbenzolsulfonate salts. The method of claim 3, wherein the sensitizer is lignin sulfonate and derivatives thereof, oxycarbonates, polyol derivatives, polyoxyethylene alkylaryl ether derivatives, alkylaryl sulfonates, formalin condensates of melamine sulfonates, formalin condensates of naphthalene sulfonates, A concrete admixture selected from the group consisting of polyamine condensates and polycarboxylic acid-based high molecular compounds. The concrete admixture according to claim 1, wherein an acrylic water-soluble polymer, metal celluloid or ethyl celluloid is included. The admixture for concrete according to claim 1, wherein the molasses fermentation by-product is organic salts are removed, and the remaining organic salts are neutralized by alkaline solution. 8. The concrete admixture according to claim 7, wherein the alkali solution is selected from the group consisting of NaOH solution, KOH solution, Ca (OH) ₂ solution, CaO solution, Mg (OH) ₂ solution and MgO solution. The admixture for concrete according to claim 7, wherein the molasses fermentation by-product is aged at 60-90 ° C. for 2-5 hours.