KR100448343B1 - Admixture for concrete comprising molasses fermentation by-product - Google Patents
Admixture for concrete comprising molasses fermentation by-product Download PDFInfo
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- KR100448343B1 KR100448343B1 KR10-2001-0068851A KR20010068851A KR100448343B1 KR 100448343 B1 KR100448343 B1 KR 100448343B1 KR 20010068851 A KR20010068851 A KR 20010068851A KR 100448343 B1 KR100448343 B1 KR 100448343B1
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- concrete
- admixture
- fermentation
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- solution
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- 238000000855 fermentation Methods 0.000 title claims abstract description 61
- 230000004151 fermentation Effects 0.000 title claims abstract description 61
- 239000006227 byproduct Substances 0.000 title claims abstract description 53
- 235000013379 molasses Nutrition 0.000 title claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- -1 polyoxymethylene Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 9
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004472 Lysine Substances 0.000 claims description 8
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 8
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims description 8
- 229920006324 polyoxymethylene Polymers 0.000 claims description 8
- 229920002160 Celluloid Polymers 0.000 claims description 6
- 229920001732 Lignosulfonate Polymers 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 229920003169 water-soluble polymer Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 125000000291 glutamic acid group Chemical group N[C@@H](CCC(O)=O)C(=O)* 0.000 claims 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 229920005610 lignin Polymers 0.000 abstract description 5
- 230000000704 physical effect Effects 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000004568 cement Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 235000001014 amino acid Nutrition 0.000 description 6
- 150000001413 amino acids Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Chemical class 0.000 description 1
- 239000004417 polycarbonate Chemical class 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/18—Waste materials; Refuse organic
- C04B18/24—Vegetable refuse, e.g. rice husks, maize-ear refuse; Cellulosic materials, e.g. paper, cork
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
본 발명은 당밀 발효 공정에서 생산되는 당밀 발효 부산물을 포함하는 콘크리트용 혼화제에 관한 것이다. 상기 당밀 발효 부산물을 포함하는 콘크리트용 혼화제는 물성면에서 기존 고가의 리그닌계 혼화제와 비교할 때 동등 이상의 성능을 보여, 혼화제 제조시 생산비 절감 효과를 얻을 수 있다. 또한, 당밀 발효 공정시 발생되는 부산물인 당밀 발효 부산물을 콘크리트에 첨가할 경우, 많은 양의 부산물을 효율적으로 재활용할 수 있기 때문에 발효 부산물의 해양 투기에 의하여 발생될 수 있는 환경오염을 줄일 수 있다는 이점이 있다.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
본 발명은 콘크리트용 혼화제에 관한 것으로서, 보다 상세하게는 당밀 발효 공정시 생산되는 유기 부산물을 포함하는 콘크리트용 혼화제에 관한 것이다.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.
콘크리트는 현대의 건축 및 토목 공사에 있어 근간을 이루는 것으로서, 콘크리트의 강도는 첨가된 재료 및 성분들이 얼마나 균질하게 혼합되어 있는가의 여부에 따라 달라진다. 이러한 측면에서, 콘크리트 제조시 사용되는 재료 및 성분들의 균질한 상태를 극대화하기 위한 혼화제의 사용 및 성능이 우수한 새로운 혼화제의 개발이 필수적이다. 최근 대형안전사고의 증가로 인하여 안전에 대한 경각심이 높아지고 있고, 건물의 대형화에 따른 콘크리트의 고강도와 고품질이 더욱 요구되고 있는 가운데 해마다 콘크리트의 제조에 있어서 혼화제의 수요량도 꾸준히 증가하고 있으며, 생산업계의 자체 기술개발이 활발히 진행되고 있다.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.
혼화제는 콘크리트에 많은 기능성을 부여하는데 물리적, 화학적 작용으로 경화중인 콘크리트나 경화된 콘크리트의 성질을 개선시키기도 하고, 경제성을 높이는 등의 목적으로 사용된다. 이러한 혼화제는 일반적으로 혼화제를 사용할 때의 효과와 용도에 따라 분류되는데 콘크리트의 공기량, 단위수량, 응결, 초기경화 속도 등에 미치는 효과에 따라 AE(air entraining agent)제, 감수제(water reducing agent), AE감수제(air entraining and water reducing agent), 고성능감수제, 유동화제, 초지연제, 수중 콘크리트용 혼화제, 방청제, 수축저감제, 수화열 억제제, 팽창제 및 방동 내한제 등으로 나뉘어진다.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.
특히, 감수제는 리그닌술폰산염계, 옥시칼본산염계, 알킬아릴술폰산염계, 멜라민술폰산염계, 폴리칼본산염계, 폴리올 유도체 등으로 분류된다. 이중, 천연계의 고분자 전해질인 리그닌술폰산염은 가장 대표적으로 사용되고 있는 혼화제로서 수중에서 리그닌술폰산 음이온과 칼슘 양이온으로 해리되는 특징을 갖고 있다. 이 음이온 부분이 시멘트 입자 표면에 흡착되어 대전층이 형성되고, 이 대전층의 정전기적 상호 반발작용에 의해 시멘트 입자는 각각 분산되어 재응집이 방지되며, 물과 공기포를 해방시킴으로써 콘크리트의 유동성이 증대된다.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.
한편, 당밀 발효 부산물은 미생물을 원료로 한 발효공정을 통해 얻어진 발효액으로부터 분리된 물질로서, 당분, 유기물, 균체, 단백질, 아미노산 등 생물의 생육에 필요한 각종 유기물과 미량 원소를 다량 함유하고 있어 비료 또는 사료로서의 이용 가치에 관심이 집중되어 왔다. 그러나, 상기 물질은 밀도 및 점성이 높아 수송, 저장 및 취급이 곤란할 뿐만 아니라, 급여시 어려움이 따르고, 농축액으로 배합사료에 첨가할 경우에도 당밀 발효 부산물 배합 비율이 일정 비율을 넘지 못하는 등의 단점으로 인해 그 사용이 제한되어 왔다.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.
또한, 최근에는 당밀 발효 부산물이 퇴비 제조시 발효 촉진제로서 사용 가능하다는 것이 알려져 사용량이 늘어나고 있지만, 이 역시 당밀 발효 부산물 함량이 20% 이상을 넘지 못하고 있는 실정이며, 농축된 당밀 발효 부산물이 동물의 사료에 일부 첨가되고 있으나 그 수량이 많지 않아 대다수의 당밀 발효 부산물은 현재 해양 투기에 의해 폐기 처리되고 있는 실정이다.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.
그러나, 상기와 같은 액상 당밀 발효 부산물의 처리 방법인 해양 투기는 바다를 오염시킬 뿐만 아니라 처리비용 자체도 막대하여 기업 및 국가 경제에 상당한 손실이 되고 있으며, 향후 수년 내에 런던협약에 의해 해양 투기 자체도 중단될 위기에 처해 있어 당밀 발효 부산물의 효율적인 처리 방안의 수립이 절실히 요구되고 있다.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.
본 발명자들은 상기 당밀 발효 부산물을 효율적으로 처리할 수 있는 방안을 연구하던 중, 상기 당밀 발효 부산물을 콘크리트용 혼화제로 사용할 경우 당밀 발효 부산물의 해양 폐기에 의한 환경 오염을 줄일 수 있을 뿐만 아니라, 콘크리트에 첨가시 우수한 감수 및 유동화 특성을 나타낸다는 사실을 확인함으로써 본 발명을 완성하게 되었다.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.
따라서, 본 발명이 이루고자 하는 기술적 과제는 유기 부산물인 당밀 발효 부산물을 적극 활용하여 콘크리트에 적용시 통상 사용되는 리그닌계 콘크리트용 혼화제보다 동등 이상의 우수한 물성을 나타낼 수는 콘크리트용 혼화제를 제공하는 것이다.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.
상기와 같은 목적을 달성하기 위하여, 본 발명은 당밀 발효 부산물을 포함하는 콘크리트용 혼화제를 제공한다.In order to achieve the above object, the present invention provides a admixture for concrete containing molasses fermentation by-products.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 있어서, 당밀 발효 부산물은 미생물을 이용하여 탄소원인 당밀로부터 아미노산; 알코올; 구연산을 포함하는 유기산; 비타민을 포함하는 생리활성 물질; 항생물질; 효소 또는 고분자 물질을 생산하는 발효 공정을 수행하고, 이후 얻어지는 발효액으로부터 목적하는 산물을 제거한 후 얻어지는 것일 수 있으며, 바람직하게는 아미노산 발효 부산물, 더욱 바람직하게는 글루탐산 또는 라이신 발효 부산물일 수 있다.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.
아미노산 발효의 예를 통해 당밀 발효 부산물의 생산 과정을 살펴보면, 먼저, 발효기에 당밀을 투입하기 전에 황산을 이용하여 당밀에서 칼슘을 제거한다. 이후, 미생물에 의해 발효를 수행하고, 다시 황산을 첨가하여 발효 반응을 중단시킨 다음, 미생물 균체(biomass)를 원심분리 등의 방법으로 제거한다. 미생물 균체를 분리한 후, 나머지 발효액으로부터 당업계에서 통상적으로 이용되는 이온 교환 수지를 이용하여 글루탐산 또는 라이신과 같은 목적 아미노산을 분리한다. 이후, 남은 부산물에는 발효에 이용되고 남은 당분, 아미노산, 단백질 등 각종 유기질과 미량 원소 등이 다량 포함되어 있으며, 이를 당밀 발효 부산물이라 한다.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.
상기 당밀 발효 부산물은 유기염류가 제거되고, 잔량의 유기염류는 알칼리 용액으로 중화된 후, 콘크리트용 혼화제에 포함되는 것이 바람직하다. 즉, 초기의 당밀 발효 부산물에는 유기염류가 있어 시멘트와 반응시 Ca(OH)2와 반응하여 암모니아 가스가 발생되므로 이러한 유기염류를 제거하는 것이 바람직하다. 상기에서 유기염류는 전기분해 방법에 의하여 제거될 수 있으며, 잔량의 유기염류를 제거하는데 사용되는 알칼리 용액은 NaOH용액, KOH용액, Ca(OH)2용액, CaO용액, Mg(OH)2용액 및 MgO용액으로 이루어진 군으로부터 선택되어 사용되는 것이 바람직하나, 이에 제한되는 것은 아니다. 또한, 상기에서 중화된 용액은 60-90℃의 온도에서 2-5시간 동안 숙성되는 것이 바람직하나, 이에 제한되는 것은 아니다.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.
한편, 상기와 같이 제조된 당밀 발효 부산물은 단독으로 혼화제로 사용될 수도 있으나, 특정 용도로 사용되는 혼화제인 AE제, 감수제 또는 이들의 혼합물과 혼합하여 사용될 수 있다. 즉, 본 발명에 따른 혼화제는 당밀 발효 부산물과 혼합되는 다른 혼화제의 종류에 따라 감수제, AE감수제, 고성능감수제, 유동화제, 수중 콘크리트용 혼화제 등의 기능으로 사용될 수 있다.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.
상기에서 당밀 발효 부산물과 함께 혼화제에 혼합될 수 있는 AE제로는 폴리옥시메틸렌 알킬에테르황산염, 폴리옥시메틸렌 알킬아릴에테르, 폴리옥시메틸렌 알킬아릴에테르의 황산에스텔 유도체, 폴리옥시메틸렌 알킬아릴에테르의 린산에스텔 유도체, 알킬아릴술폰산염 또는 알킬벤졸술폰산염일 수 있으나, 이에 제한되는 것은 아니다.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.
또한, 당밀 발효 부산물과 함께 혼화제에 혼합될 수 있는 감수제로는 리그닌술폰산염 및 그 유도체, 옥시칼본산염, 폴리올 유도체, 폴리옥시에틸렌 알킬아릴에테르 유도체, 알킬아릴술폰산염, 멜라민 술폰산염의 포르말린 축합물, 나프탈렌 술폰산염의 포르말린 축합물, 폴리아민 축합물 또는 폴리칼본산계 고분자 화합물일 수 있으나, 이에 제한되는 것은 아니다.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.
한편, 본 발명에 따른 콘크리트용 혼화제에는 상기 AE제, 감수제 또는 이들의 혼합물과 함께 고급 지방 알콜계 분산제가 추가로 첨가될 수 있다.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.
또한, 본 발명에 따른 콘크리트용 혼화제는 아크릴계 수용성 폴리머, 메탈 셀룰로이드, 에틸 셀룰로이드 또는 이들의 혼합물과 혼합하여 제조될 수 있다.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.
본 발명에 따른 당밀 발효 부산물을 포함하는 콘크리트용 혼화제는 친수성기인 카르복실기와 아민기가 다량 함유되어 있어, 시멘트 사이의 대전층의 전위가 비슷한 입자 사이에 전기적 상호 반발력을 발생시킨다. 이에 따라, 시멘트 입자가 고르게 분산됨으로써 시멘트의 유동성이 크게 증가하게 되고, 결국 콘크리트의 유동성이 향상된다는 이점이 있다.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.
본 발명에 따른 혼화제에 첨가되는 당밀 발효 부산물의 양은 경제적인 측면을 고려하여 적정량으로 첨가될 수 있다. 즉, 기존 고가의 AE제, 감수제 또는 이들의 혼합물에 소량으로 첨가될 수도 있지만, 생산 단가의 절감을 위해서는 다음과 같은 혼합비율로 첨가되는 것이 바람직하다.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.
구체적으로 본 발명에 따른 혼화제는 당밀 발효 부산물 80-90중량%, 술폰산염계 화합물 9-19.5중량% 및 알킬벤졸술폰산염계 AE제 0.5-1중량%를 포함한 AE감수제로 제조될 수 있으나, 이에 제한되는 것은 아니다. 또한, 본 발명에 따른 혼화제는 당밀 발효 부산물 80-85중량%, 아크릴계 수용성 폴리머 10-17중량%, 메탈 셀룰로이드 1-4중량% 및 알킬벤졸술폰산염계 AE제 0.5-1중량%를 포함한 유동화제로 제조될 수 있으나, 이에 제한되는 것은 아니다.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.
이하, 본 발명을 실시예에 의해 상세히 설명한다.Hereinafter, the present invention will be described in detail by way of examples.
단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.
<제조예 1><Manufacture example 1>
라이신 당밀 발효 부산물 500g을 반응기에 넣은 다음, 80℃의 온도에서 180rpm으로 교반하였다. 교반과 동시에 KOH(물 1000g + KOH 1000g)용액 200g을 3분간에 걸쳐 적하시키면서, 5시간 동안 숙성시켰고, 이후, 상온까지 냉각시켜 콘크리트용 혼화제를 제조하였다.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.
<제조예 2><Manufacture example 2>
제조예 1의 라이신 당밀 발효 부산물 80중량%, 리그닌술폰산염(석현사, 중국) 18.5중량%, 알킬벤졸술폰산염계 AE제(애경화학) 1중량%, 고급 지방 알콜계 분산제(애경화학) 0.5중량%를 혼합한 후, 60℃에서 2시간 동안 반응시켜 콘크리트용 AE감수제 조성물을 제조하였다.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.
<제조예 3><Manufacture example 3>
제조예 1의 라이신 당밀 발효 부산물 80중량%, 지연형 나프탈렌 술폰산염 포르말린(경기화학) 19중량% 및 알킬벤졸술폰산염계 AE제(애경화학) 1중량%를 혼합한 후, 60℃에서 2시간 동안 반응시켜 콘크리트용 AE감수제 조성물을 제조하였다.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.
<제조예 4><Manufacture example 4>
제조예 1의 라이신 당밀 발효 부산물 90중량%, 지연형 멜라민 술폰산염 포르말린계(perstorp SA사, 프랑스) 9중량% 및 알킬벤졸술폰산염계 AE제(애경화학) 1중량%를 혼합한 후, 60℃에서 2시간 동안 반응시켜 콘크리트용 AE감수제 조성물을 제조하였다.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.
<제조예 5>Production Example 5
라이신 당밀 발효 부산물 80중량%, 아크릴계 수용성 폴리머(LG화학) 17중량% 및 메탈셀룰로이드(삼성화학) 3중량%를 혼합한 후, 60℃에서 2시간 동안 반응시켜 콘크리트용 유동화제 조성물을 제조하였다.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.
<비교예 1>Comparative Example 1
리그닌술폰산염(석현사, 중국) 98.5중량%, 알킬벤졸술폰산염계 AE제(애경화학) 1중량%, 고급 지방 알콜계 분산제(삼성화학) 0.5중량%를 혼합한 후, 60℃에서 2시간 동안 반응시켜 콘크리트용 AE감수제 조성물을 제조하였다.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.
<비교예 2>Comparative Example 2
나프탈렌 술폰산염 포르말린(경기화학) 99중량%, 알킬벤졸술폰산염계 AE제(애경화학) 1중량%를 혼합한 후, 60℃에서 2시간 동안 반응시켜 콘크리트용 AE감수제 조성물을 제조하였다.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.
<실시예 1><Example 1>
콘크리트의 제조 및 물성 비교Preparation of concrete and comparison of properties
시멘트 320kg, 물 176kg, 굵은골재 1003kg 및 잔골재 746kg을 혼합한 후, 상기 제조예 1 내지 5 및 비교예 1 또는 2에서와 같이 제조한 각 콘크리트용 혼화제를 시멘트의 0.5중량%의 함량(1.6kg)으로 혼합하여 콘크리트를 제조하였으며, 이와 같이 제조된 각 콘크리트들의 물성을 KS F 2560에 따라 비교하여 하기 표 1에 기재하였다.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.
* 감수율 : 물/시멘트 x 100으로 계산되는 값의 감소치를 의미한다.* Susceptibility rate: It means the decrease value calculated by water / cement x 100.
** 재령 : 콘크리트 혼합물을 거푸집에 충전시킨 후의 방치 기간을 의미한다.** Age: The standing period after filling the formwork with concrete mixture.
상기 표 1에 기재된 바와 같이, 감수율의 경우 제조예 1 내지 5에서 제조한 본 발명의 당밀 발효 부산물 혼화제를 첨가한 콘크리트가 비교예 1에서 제조한 기존 리그닌계 혼화제를 첨가한 콘크리트에 비해 높음을 알 수 있고, 비교예 2에서 제조한 기존 나프탈렌계 혼화제를 첨가한 콘크리트와 거의 같은 성능을 보이고 있다.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.
또한, 블리딩량의 경우 본 발명에 따른 당밀 발효 부산물 혼화제를 첨가한 콘크리트가 약 65% 전후로서 혼화제를 첨가하지 않은 콘크리트에 비해 수치가 낮음을 확인할 수 있었다. 즉, 본 발명에 따른 혼화제를 사용하는 경우 재료 분리가 잘 일어나지 않기 때문에 콘크리트 제조시 흔히 발생되는 블리딩에 의한 악영향을감소시킬 수 있음을 확인할 수 있었다.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.
한편, 콘크리트의 응결시간의 차를 비교한 결과, 본 발명에 따른 혼화제를 첨가한 콘크리트가 비교예 1 및 비교예 2에서 제조한 혼화제를 첨가한 콘크리트에 비해 수화가 늦게 일어남을 알 수 있었다. 즉, 본 발명에 따른 혼화제를 첨가하는 경우 콘크리트의 응결정도가 지연됨을 확인할 수 있었다.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.
콘크리트의 압축강도 비를 보면, 본 발명에 따른 혼화제를 첨가한 콘크리트의 압축강도가 비교예 1에서 제조한 혼화제를 첨가한 콘크리트의 압축강도에 비해 약 10-16% 증가하였음을 확인할 수 있었다.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.
또한, 길이 변화나 동결융해에 대한 저항성을 테스트한 결과에서도 기존의 혼화제를 첨가한 콘크리트에 비해 동등이상의 성능을 발휘하는 것으로 나타났다.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.
본 발명에 따른 당밀 발효 부산물을 포함하는 콘크리트용 혼화제는 물성면에서 기존 고가의 리그닌계 혼화제와 비교할 때 동등 이상의 성능을 갖고 있어 경제적인 면에 있어 생산비 절감 효과를 얻을 수 있다. 또한, 발효 공정시 발생되는 당밀 발효 부산물을 콘크리트에 첨가할 경우, 많은 양의 부산물을 효율적으로 재활용할 수 있기 때문에 발효 부산물의 해양 투기에 의하여 발생될 수 있는 환경오염을 줄일 수 있다는 이점이 있다.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.
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| JP2007537117A (en) * | 2004-05-14 | 2007-12-20 | オーストレリアン インダストリアル アディティブズ ピーティーワイ リミテット | Molasses treatment method for producing "Molasspers" surfactant for use in concrete fluidizer (water reducing agent) and cement clinker grinding admixture |
| DE102005055617A1 (en) * | 2005-11-22 | 2007-05-31 | Degussa Ag | Use of protein hydrolyzates originating from biomass as additives in hydraulically hardenable compositions |
| CA2839376C (en) | 2011-06-24 | 2019-02-26 | Construction Research & Technology Gmbh | Cement additive |
| EP2723694A1 (en) * | 2011-06-24 | 2014-04-30 | Construction Research & Technology GmbH | Cementitious composition and admixture |
| KR101341056B1 (en) * | 2012-01-13 | 2013-12-11 | 손재호 | Manufacturing method of concrete admixture using molasses sludge |
| KR101690928B1 (en) * | 2015-08-10 | 2016-12-30 | 주식회사 에스앤피글로벌 | Manufacturing method of concrete admixture using cornsyrup and/or liquid sugar |
| KR101646105B1 (en) * | 2015-12-01 | 2016-08-09 | 주식회사 조일콘크리트 | Eco Concrete Compositions and Products using Growth Promoting Substances |
| KR102735969B1 (en) * | 2022-10-21 | 2024-12-03 | 주식회사 실크로드시앤티 | Additive for concrete comprising polycarboxylate ether-based copolymer compound prepared by reacting different macro monomers and chemical admixture for concrete comprising the same |
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