KR100963822B1 - An admixture for concrete, prepared using black liquor from pulping process, and a method for preparation of the same - Google Patents
An admixture for concrete, prepared using black liquor from pulping process, and a method for preparation of the same Download PDFInfo
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- 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
- C04B18/241—Paper, e.g. waste paper; Paper pulp
- C04B18/243—Waste from paper processing or recycling paper, e.g. de-inking sludge
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- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/068—Peroxides, e.g. hydrogen peroxide
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- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/149—Iron-sulfates
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/304—Air-entrainers
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/50—Defoamers, air detrainers
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/63—Flame-proofing agents
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Abstract
본 발명은 펄프 제조시 발생된 흑액으로부터 제조된 콘크리트용 혼화제 및 이의 제조방법에 관한 것으로, 더욱 상세하게는 펄프 제조 시 발생된 흑액을 오존, 과산화수소, 펜톤시약 등의 산화제로 산화 처리함으로써 외부 박테리아에 의해 일어나는 부패를 방지할 수 있고, 콘크리트용 혼화제로 이용 시 굳지 않는 콘크리트의 응결지연의 원인이 되는 리그닌, 목당(-OH) 성분을 산화반응을 이용하여 알테히드(-COH), 케톤(-COR) 또는 카르복실기(-COOH)로 전환 유도하여 응결지연성이 없는 콘크리트용 혼화제에 관한 것이다.The present invention relates to a concrete admixture prepared from black liquor generated during pulp production and a method for preparing the same. More specifically, the black liquor produced during pulp production is oxidized with an oxidizing agent such as ozone, hydrogen peroxide, fenton reagent, etc. It is possible to prevent the decay caused by the oxidizing reaction of lignin and wood sugar (-OH), which causes the coagulation delay of concrete that does not harden when used as a concrete admixture, by using aldehyde (-COH) and ketone (-COR). Or to a carboxyl group (-COOH), and relates to a concrete admixture having no coagulation delay.
흑액, 펄프, 콘크리트, 혼화제, 분산성, 강도, 부패 방지 Black liquor, pulp, concrete, admixture, dispersibility, strength, anti-rot
Description
본 발명은 펄프 제조시 발생된 흑액으로부터 제조된 콘크리트용 혼화제 및 이의 제조방법에 관한 것으로, 더욱 상세하게는 펄프 제조 시 발생된 흑액을 오존, 과산화수소, 펜톤시약 등의 산화제로 산화 처리함으로써 외부 박테리아에 의해 일어나는 부패를 방지할 수 있고, 콘크리트용 혼화제로 이용 시 굳지 않는 콘크리트의 응결지연의 원인이 되는 리그닌, 목당(-OH) 성분을 산화반응을 이용하여 알테히드(-COH), 케톤(-COR) 또는 카르복실기(-COOH)로 전환 유도하여 응결지연성이 없는 콘크리트용 혼화제에 관한 것이다.The present invention relates to a concrete admixture prepared from black liquor generated during pulp production and a method for preparing the same. More specifically, the black liquor produced during pulp production is oxidized with an oxidizing agent such as ozone, hydrogen peroxide, fenton reagent, etc. It is possible to prevent the decay caused by the oxidizing reaction of lignin and wood sugar (-OH), which causes the coagulation delay of concrete that does not harden when used as a concrete admixture, by using aldehyde (-COH) and ketone (-COR). Or to a carboxyl group (-COOH), and relates to a concrete admixture having no coagulation delay.
종이를 만드는 원료인 펄프를 제조하는 과정을 펄핑(pulping)이라 하는데, 펄핑과정은 목재의 구성성분인 셀룰로오즈, 헤미셀룰로오즈, 리그닌, 기타 추출물 등으로 구성된 혼합물로부터 셀룰로오즈를 제외한 나머지 성분들을 제거하는 공정이다. 이렇게 헤미셀룰로오즈, 리그닌 등을 제거하는 펄핑 방법에는 기계펄핑, 화학펄핑, 반화학펄핑 등이 있으며, 이중 화학펄핑법은 화학 약품을 첨가하여 펄프화 하는 방법으로 대표적으로 크라프트 펄핑(kraft pulping)과 설파이트 펄핑(sulfite pulping)이 있다. 펄핑 과정에서 셀룰로오즈를 제외하고 제거되는 나머지 물질을 포함한 폐액을 일반적으로 흑액(black liquor)이라 한다. The process of manufacturing pulp, the raw material for making paper, is called pulping.Pulping is the process of removing cellulose from the mixture of cellulose, hemicellulose, lignin, and other extracts of wood. . Such pulping methods for removing hemicellulose and lignin include mechanical pulping, chemical pulping and anti-chemical pulping, and double chemical pulping is a method of pulping by adding chemicals. There is sulfite pulping. Waste liquor containing the remaining material removed except cellulose in the pulping process is commonly referred to as black liquor.
크라프트 펄프 제조과정에서 발생하는 흑액 속에는 고분자 물질인 리그닌(목당)이 다량 함유되어 있으나, 현재로서는 추가 공정을 거치지 않고 태워서 열원으로 이용하거나 증발 잔류 약품을 회수하여 증해액으로 재이용하고 있을 뿐이다. The black liquor produced during the production of kraft pulp contains a large amount of lignin (wood sugar), which is a high-molecular substance, but currently, it is burned without further processing and used as a heat source or the evaporation residual chemical is recovered and reused as a cooking liquor.
일반적으로 흑액 속에는 다량의 리그닌을 함유하고 있어 콘크리트용 혼화제로 사용될 수 있으나 대기중 방치시 외부 박테리아에 의해 부패되어 분산기능을 상실하는 것으로 알려져 있다. 또한 리그닌을 콘크리트용 혼화제로 사용할 경우 리그닌의 콘크리트 응결지연 현상에 의해 그 사용량이 제한되고 있다.In general, the black liquor contains a large amount of lignin, which can be used as a concrete admixture, but it is known to lose its dispersing function due to corruption by external bacteria when left in the air. In addition, when lignin is used as a concrete admixture, the amount of lignin is limited due to the delay of concrete coagulation.
종래 펄프 제조시 발생된 폐기물 즉, 흑액을 재이용하기 위한 방법에 관한 특허문헌으로는 대한민국 등록특허 제10-0385580호에 흑액을 필요에 따라 과산화수소, 차아염소산소다등으로 탈색과 묽은 황산 및 연한 기타 산으로 필요한 산, 알카리 수준을 조정하고 증발 및 수분 첨가로 필요한 수준의 농도를 조정한 뒤 방부제를 중량대비 0.1 ∼ 1% 첨가하여 사용하는 방법이 개시되어 있다.As a patent document on a method for reusing waste, namely, black liquor, which is produced during the manufacture of a conventional pulp, the black liquor is disclosed in Korean Patent No. 10-0385580 with hydrogen peroxide, sodium hypochlorite, and the like. It is disclosed a method of adjusting the required acid and alkali levels, and adjusting the concentration of the required level by evaporation and water addition, and then adding 0.1 to 1% by weight of a preservative.
그러나, 상기 방법은 방부제를 별도로 첨가함으로써 부패는 방지할 수 있으나 흑액 속에 함유되어 있는 리그닌, 목당(-OH) 성분으로 인하여 콘크리트용 혼화제로 이용 시 굳지 않는 콘크리트의 응결지연의 원인이 되어 앞서 기재한 바와 같이 그 사용량에 제한이 있는 단점이 있다.However, the method can prevent the decay by adding a preservative separately, but due to the lignin and wood sugar (-OH) contained in the black liquor, which causes the coagulation delay of the concrete that does not harden when used as a concrete admixture, As described above, there is a disadvantage in that the usage is limited.
이에 본 발명자는 상기와 같은 종래 기술의 단점을 극복할 수 있도록 연구한 결과, 펄프 제조 시 발생된 흑액을 오존, 과산화수소, 펜톤시약 등의 산화제로 산화 처리함으로써 외부 박테리아에 의해 일어나는 부패를 방지할 수 있고, 콘크리트용 혼화제로 이용 시 굳지 않는 콘크리트의 응결지연의 원인이 되는 리그닌, 목당(-OH) 성분을 산화반응을 이용하여 알테히드(-COH), 케톤(-COR) 또는 카르복실기(-COOH)로 전환 유도하여 응결지연성이 없는 콘크리트용 혼화제를 제조할 수 있음을 확인함으로써 본 발명을 완성하게 되었다.Accordingly, the present inventors have studied to overcome the disadvantages of the prior art as described above, by oxidizing the black liquor generated during the manufacture of pulp with an oxidizing agent such as ozone, hydrogen peroxide, fenton reagent, etc. to prevent corruption caused by external bacteria. And lignin and wood sugar (-OH), which cause the coagulation delay of concrete that does not harden when used as a concrete admixture, by oxidizing the aldehyde (-COH), ketone (-COR) or carboxyl group (-COOH) The present invention has been completed by confirming that the admixture for concrete having no condensation delaying effect can be produced by inducing conversion to.
본 발명의 목적은 펄프 제조 시 발생된 흑액을 오존, 과산화수소, 펜톤시약 등의 산화제로 산화 처리함으로써 외부 박테리아에 의해 일어나는 부패를 방지할 수 있고, 응결지연성이 없는 콘크리트용 혼화제를 제조하는 방법을 제공하고자 하는 것이다.An object of the present invention is to oxidize the black liquor generated during the production of pulp with an oxidizing agent such as ozone, hydrogen peroxide, fenton reagent, etc. to prevent the decay caused by external bacteria, and to prepare a concrete admixture having no coagulation delay. It is to provide.
본 발명의 다른 목적은 상기 방법으로 제조된 콘크리트용 혼화제를 제공하고자 하는 것이다.Another object of the present invention is to provide a admixture for concrete produced by the above method.
하나의 양태로서, 본 발명은 펄프 제조 시 발생된 흑액을 산화제로 산화 처리하여 제조되는 콘크리트용 혼화제의 제조방법을 제공한다.In one aspect, the present invention provides a method for producing a admixture for concrete prepared by oxidizing the black liquor generated during pulp production with an oxidizing agent.
이하, 본 발명의 구성을 상세히 설명한다.Hereinafter, the configuration of the present invention will be described in detail.
콘크리트 분산제의 첨가량에 따른 굳지 않은 콘크리트의 분산성을 설명하는 대표적인 이론으로는 입자간 전기적 반발력에 의해서 분산 안정성을 이루는 DLVO(Derjagunin Landau Verway Overbeek)이론과 분산제의 구조, 흡착형태와 흡착층의 두께 등에 의한 입체적 반발력에 의해서 입자의 분산안정성이 유지된다는 입체효과 이론으로 설명되어진다.Representative theories explaining the dispersibility of unconsolidated concrete according to the amount of added concrete dispersant include the theory of DLVO (Derjagunin Landau Verway Overbeek) which achieves dispersion stability by electrical repulsive force between particles, the structure of dispersant, the adsorption type and the thickness of the adsorption layer. By the three-dimensional repulsive force by the three-dimensional effect theory that the dispersion stability of the particles is maintained.
즉, NSF계 및 멜라민계 분산제는 시멘트 입자표면에 봉 형태로 여러 층 흡착되고, 화학구조 중에 결합되어 있는 설폰산기의 음(-)이온이 나타내는 강력한 정전 기적 반발력에 의해서 시멘트 입자가 분산된다. 그러나 폴리카르본산계 분산제는 화학구조 중에 결합되어 있는 카르복실기의 음(-)이온에 의한 정전기적 반발력과 주쇄 혹은 측쇄에 의한 입체효과가 상승적으로 작용하여 시멘트 입자가 분산되는 효과를 얻게 된다.That is, NSF-based and melamine-based dispersants are adsorbed on the surface of cement particles in the form of rods, and the cement particles are dispersed by the strong electrostatic repulsion force indicated by the negative ions of sulfonic acid groups bonded in the chemical structure. However, the polycarboxylic acid-based dispersant has a synergistic effect of the electrostatic repulsion by the negative (-) ions of the carboxyl groups bonded in the chemical structure and the steric effect by the main chain or side chains to obtain the effect of the cement particles dispersed.
본 발명에서는 크라프트 펄프 제조 공정에서 발생하는 흑액 속의 헤미셀룰로오즈와 리그닌 등의 친수성 유기물들을 산화시킴으로서 흑액의 부패에 따른 물성 저하 방지 및 헤미셀룰로오즈나 리그닌 구조 중에 카르복실기 및 하이드록시기 등을 형성시켜 당 성분에 의한 콘크리트 응결지연 억제 그리고 카르복실기의 음(-) 이온에 의한 정전기적 반발력 및 하이드록시기의 수소결합, 주쇄 혹은 측쇄에 의한 입체효과가 상승적으로 작용하여 시멘트 입자의 분산성이 향상되는 효과를 얻고자 하는 것을 특징으로 하고 있다.In the present invention, by oxidizing hydrophilic organic substances such as hemicellulose and lignin in black liquor generated in kraft pulp manufacturing process, prevention of deterioration of physical properties due to corruption of black liquor and formation of carboxyl group and hydroxyl group in hemicellulose or lignin structure In order to achieve the effect of improving the dispersibility of cement particles by suppressing the concrete coagulation delay by the negative effect, the electrostatic repulsion by the negative ions of the carboxyl group and the steric effect by the hydrogen bond, the main chain or the side chain of the hydroxy group It is characterized by.
본 발명에서, 흑액은 제조되는 콘크리트용 혼화제의 전체 중량%에서 5 내지 95중량%, 바람직하게는 30 내지 95중량%, 더욱 바람직하게는 50 내지 95중량%를 사용한다.In the present invention, the black liquor uses 5 to 95% by weight, preferably 30 to 95% by weight, more preferably 50 to 95% by weight, based on the total weight of the admixture for concrete prepared.
본 발명의 바람직한 양태로서, 상기 흑액의 산화 처리에서 사용하는 산화제로는 오존(O3), H2O2, 펜톤시약(황산제1철과 과산화수소), KMnO4, K2Cr2O7, K2S2O8, 전자빔 및 방사선으로 이루어진 군으로부터 선택되는 어느 하나 이상의 산화제를 이용할 수 있으며, 이에 제한되지 않는다.In a preferred embodiment of the present invention, the oxidizing agent used in the oxidation treatment of the black liquor includes ozone (O 3 ), H 2 O 2 , fenton reagent (ferrous sulfate and hydrogen peroxide), KMnO 4 , K 2 Cr 2 O 7 , K 2 S 2 O 8 , Any one or more oxidants selected from the group consisting of electron beams and radiations can be used, but are not limited thereto.
본 발명에서는 일 실시예로서 오존, 그리고 펜톤시약을 이용하여 콘크리트용 혼화제를 제조한다.In the present invention, an admixture for concrete is prepared using ozone and Fenton reagent as an embodiment.
본 발명의 바람직한 양태로서, 산화제로 오존을 사용할 경우 오존의 처리는 흑액 100 g에 대하여 오존을 5.0 mg/1min 내지 20.0 mg/1min의 속도로 10~200분 동안 처리함으로써 수행할 수 있으며, 가장 바람직하기로는 오존을 10.0 mg/1min의 속도로 100분 동안 처리함으로써 수행하는 것이 좋다.As a preferred embodiment of the present invention, when ozone is used as the oxidizing agent, the treatment of ozone may be performed by treating ozone at a rate of 5.0 mg / 1 min to 20.0 mg / 1 min for 10 to 200 minutes with respect to 100 g of black liquor, most preferably. It is preferable to carry out by treating ozone for 100 minutes at a rate of 10.0 mg / 1 min.
본 발명에서, 산화제로 펜톤시약을 사용할 경우 흑액의 산화 처리는 흑액에 황산제1철(FeSO4) 또는 황산제2철(Fe2(SO4)3)을 적하하여 교반한 다음 상기 교반액에 과산화수소를 적하하여 다시 교반한 후 얻은 혼합물을 산화반응시킴으로써 수행될 수 있다.In the present invention, in the case of using the Fenton reagent as the oxidizing agent, the oxidation treatment of the black liquid is added dropwise to the black liquid ferric sulfate (FeSO 4 ) or ferric sulfate (Fe 2 (SO 4 ) 3 ) and stirred and then added to the stirring solution Hydrogen peroxide can be added dropwise and stirred again, followed by oxidation of the mixture obtained.
본 발명에서, 상기 펜톤시약을 이용한 산화 처리 시 흑액과 산화제의 혼합물의 산화반응은 20 내지 100 ℃의 온도에서 수행할 수 있다.In the present invention, the oxidation reaction of the mixture of the black liquid and the oxidizing agent in the oxidation treatment using the Fenton reagent may be carried out at a temperature of 20 to 100 ℃.
본 발명에서, 상기 펜톤시약을 이용한 산화 처리 시 흑액과 산화제의 혼합물의 산화반응은 1분 이상 동안, 바람직하기로는 1분 내지 3시간 동안 수행할 수 있으나, 이에 제한되지 않는다.In the present invention, the oxidation reaction of the mixture of the black liquid and the oxidizing agent during the oxidation treatment using the Fenton reagent may be performed for at least 1 minute, preferably 1 minute to 3 hours, but is not limited thereto.
본 발명의 바람직한 일 실시예로서, 상기 흑액과 산화제의 혼합물의 산화반응은 50℃에서 20분 동안 수행한다.In a preferred embodiment of the present invention, the oxidation reaction of the mixture of the black liquid and the oxidizing agent is carried out at 50 ℃ for 20 minutes.
본 발명의 바람직한 양태로서, 상기 황산제1철은 분산성 및 강도증진 효과면에 있어서 흑액 100 g에 대하여 0.1 내지 10g 첨가할 수 있으며, 더욱 바람직하기 로는 1 내지 5g, 가장 바람직하기로는 1 g을 첨가하는 것이 좋다.As a preferred embodiment of the present invention, the ferrous sulfate may be added in an amount of 0.1 to 10 g with respect to 100 g of black liquor in terms of dispersibility and strength enhancing effect, more preferably 1 to 5 g, most preferably 1 g It is good to add.
본 발명의 바람직한 양태로서, 상기 황산제2철은 분산성 및 강도증진 효과면에 있어서 흑액 100 g에 대하여 0.1 내지 10g 첨가할 수 있으며, 더욱 바람직하기로는 1 내지 5g, 가장 바람직하기로는 1 g을 첨가하는 것이 좋다.As a preferred embodiment of the present invention, the ferric sulfate may be added in an amount of 0.1 to 10 g with respect to 100 g of black liquor in terms of dispersibility and strength enhancing effect, more preferably 1 to 5 g, most preferably 1 g It is good to add.
또한, 본 발명의 바람직한 양태로서, 상기 과산화수소는 분산성 및 강도증진 효과면에 있어서 흑액 100 g에 대하여 0.5 ml 내지 30 ml를 첨가할 수 있으며, 더욱 바람직하기로는 10 ml 내지 20 ml, 가장 바람직하기로는 10 ml를 첨가하는 것이 좋다.In addition, as a preferred embodiment of the present invention, the hydrogen peroxide may be added 0.5 ml to 30 ml with respect to 100 g of black liquor in terms of dispersibility and strength enhancing effect, more preferably 10 ml to 20 ml, most preferably It is recommended to add 10 ml.
하나의 바람직한 양태로서, 본 발명은 펄프 제조 시 발생된 흑액을 산화제로 산화 처리하는 단계; 및 공기연행제, 슬럼프유지제, 소포제, 급결제, 지연제, 블리딩억제제, 감수제, 방향제 및 내화제로 이루어진 군으로부터 선택된 어느 하나 이상의 첨가제를 추가로 혼합하는 단계를 포함하는 콘크리트용 혼화제의 제조방법을 제공할 수 있다.In one preferred embodiment, the present invention comprises the steps of oxidizing the black liquor generated during pulp preparation with an oxidant; And further mixing any one or more additives selected from the group consisting of an air entrainer, a slump holding agent, an antifoaming agent, a fastening agent, a retardant, a bleeding inhibitor, a water reducing agent, an air freshener, and a fireproofing agent. Can provide.
상기 공기연행제, 슬럼프유지제, 소포제, 급결제, 지연제, 블리딩억제제, 감수제, 방향제 또는 내화제는 제조되는 콘크리트용 혼화제의 용도에 적합하게 하나 이상 선택하여 사용할 수 있다. 예를 들어, 본 발명에 의해 제조된 콘크리트용 혼화제에 공기연행효과를 부여하기 위해 공기연행제를 첨가하고, 슬럼프유지성능을 부여하기 위해 슬럼프유지제를, 그리고 소포작용을 부여하기 위해 소포제를, 콘크리트의 급결을 유도하기 위해 급결제를, 콘크리트의 응결 지연작용을 유도하기 위 해 지연제를, 큰크리트의 블리딩현상을 억제하기 위해 블리딩억제제를, 감수율을 증가시키기 위해 감수제 등을 첨가하는 것이다. 상기 공기연행제, 슬럼프유지제, 소포제, 급결제, 지연제, 블리딩억제제, 감수제, 방향제 및 내화제는 상업적으로 판매되는 제품을 사용할 수 있다. The air entraining agent, the slump holding agent, the antifoaming agent, the quickening agent, the retarding agent, the bleeding inhibitor, the water reducing agent, the fragrance or the refractory agent can be selected and used suitably for the use of the admixture for concrete to be produced. For example, an air entrainer is added to the admixture for concrete prepared by the present invention to impart an air entraining effect, a slump retainer to impart slump retention performance, and an antifoaming agent to impart an antifoaming action. Add a fastener to induce concrete quenching, a retardant to induce condensation retardation of concrete, a bleeding inhibitor to suppress bleeding of large concrete, and a water reducing agent to increase the susceptibility. The air entraining agent, the slump holding agent, the antifoaming agent, the fastening agent, the retardant, the bleeding inhibitor, the water reducing agent, the fragrance and the refractory agent may use a commercially available product.
본 발명의 바람직한 양태로서, 상기 첨가제는 콘크리트용 혼화제의 전체 중량%에서 0.5 내지 95 중량%의 비율로 포함된다.In a preferred embodiment of the present invention, the additive is included in the proportion of 0.5 to 95% by weight in the total weight of the admixture for concrete.
다른 하나의 양태로서, 본 발명은 상기 제조방법에 의하여 제조된 콘크리트용 혼화제를 제공한다.As another aspect, the present invention provides a admixture for concrete produced by the above production method.
본 발명의 상기 방법에 의하여 제조된 콘크리트용 혼화제는 본 발명의 제조 방법을 거치지 않는 흑액 원액에 비하여 콘크리트 처리 시 더욱 높은 분산성과 더욱 작은 슬럼프 손실을 나타내고 아울러 더욱 높은 기계적 강도를 보임을 특징으로 한다. The admixture for concrete prepared by the above method of the present invention is characterized by higher dispersibility and smaller slump loss during concrete treatment and higher mechanical strength than the black liquor stock solution which does not go through the production method of the present invention.
본 발명은 펄프 제조 시 발생된 흑액을 오존, 과산화수소, 펜톤시약 등의 산화제로 산화 처리함으로써 외부 박테리아에 의해 일어나는 부패가 방지되고, 응결지연성이 없는 콘크리트용 혼화제를 제조하는 방법을 제공할 수 있다. 또한, 상기와 같이 간단한 처리를 통해 펄프 제조 과정에서 발생하는 폐액인 흑액을 콘크리트용 혼화제로서 재이용할 수 있어 경제적 면에서도 매우 효과적이다.The present invention can provide a method of preparing a admixture for concrete that is prevented from rot caused by external bacteria by oxidizing black liquid generated during the manufacture of pulp with an oxidizing agent such as ozone, hydrogen peroxide, fenton reagent, and the like without condensation delay. . In addition, through the simple treatment as described above, the black liquor, which is a waste liquid generated in the pulp manufacturing process, can be reused as a concrete admixture, which is very economically effective.
이하, 실시예 및 제조예를 통해 본 발명을 상세히 설명하면 다음과 같다. 하기 실시예 및 제조예는 단지 본 발명을 보다 구체적으로 설명하기 위한 것으로서 본 발명을 이에 제한하고자 함이 아니다.Hereinafter, the present invention will be described in detail with reference to Examples and Preparation Examples. The following examples and preparations are merely intended to illustrate the present invention in more detail and are not intended to limit the present invention thereto.
실시예Example 1 One
크라프트 펄프 과정 중 발생하는 용액 상태의 물질 즉, 흑액 100g에 황산제1철(FeSO4) 1.0g을 넣어 5분 동안 교반한 후 과산화수소(H2O2, 35%) 10ml를 서서히 적하하여 5분간 교반하였다. 이후 상기 혼합물은 서서히 50℃까지 가열하여 20분 정도 반응시킨 뒤 최종생성물을 얻었다. 1.0 g of ferrous sulfate (FeSO 4 ) was added to 100 g of black liquor, that is, a solution material generated during kraft pulp, and stirred for 5 minutes. Then, 10 ml of hydrogen peroxide (H 2 O 2 , 35%) was slowly added dropwise for 5 minutes. Stirred. Thereafter, the mixture was slowly heated to 50 ° C. and reacted for about 20 minutes to obtain a final product.
실시예Example 2 2
실시예 2는 상기 실시예 1과 동일한 시료와 동일 조건에서 수행하되, 황산제1철을 5g으로 하여 최종생성물을 얻었다.Example 2 was carried out under the same conditions as in Example 1, except that 5 g of ferrous sulfate was used to obtain a final product.
실시예Example 3 3
실시예 3은 상기 실시예 1과 동일한 시료와 동일 조건에서 수행하되, 과산화수소를 20ml로 하여 최종생성물을 얻었다.Example 3 was carried out under the same conditions as in Example 1, except that 20 ml of hydrogen peroxide was used to obtain a final product.
실시예Example 4 4
실시예 4는 상기 실시예 1과 동일한 시료와 동일 조건에서 수행하되, 황산제1철을 투입하는 대신 황산제2철(Fe2(SO4)3)을 1g 투입하여 최종생성물을 얻었다.Example 4 was carried out under the same conditions as in Example 1, except that 1 g of ferric sulfate (Fe 2 (SO 4 ) 3 ) was added instead of ferrous sulfate to obtain a final product.
실시예Example 5 5
실시예 5는 상기 실시예 1과 동일한 시료와 동일 조건에서 수행하되, 황산제1철과 과산화수소를 첨가하는 대신에 길이는 30cm, 직경이 2cm인 투명아크릴로 제작된 반응조에 흑액 100g을 주입한 후 오존 10.0mg/lmin으로 오존과 시료의 접촉시간을 100분으로 하여 최종생성물을 얻었다. Example 5 was carried out under the same conditions as in Example 1, but instead of adding ferrous sulfate and hydrogen peroxide, 100 g of black liquor was injected into a reaction vessel made of transparent acrylic having a length of 30 cm and a diameter of 2 cm. The final product was obtained at a contact time between ozone and the sample at 10.0 mg / lmin and 100 minutes.
제조예Production Example 1 : 콘크리트 제조 및 물성 비교 1: Concrete Preparation and Property Comparison
상기 실시예 1-5에서 제조된 시료들과 산화처리를 하지 않은 흑액 원액을 대상으로 콘크리트의 슬럼프, 공기량 및 강도에 대한 효과를 확인하기 위하여 콘크리트에 이들을 첨가하여 성능검사를 수행하여, 그 시험결과를 표 1에 나타내었다.In order to confirm the effects on the slump, air volume and strength of concrete, the samples prepared in Example 1-5 and the untreated black liquor were subjected to a performance test by adding them to concrete, and the test results. Is shown in Table 1.
시험에 사용한 재료 및 콘크리트 배합은 쌍용시멘트사 보통 포틀랜트 시멘트 365kg, 모래는 강사 891kg, 굵은골재 934kg 및 시멘트 혼화제를 포함한 물 157kg이다. 각 시멘트 혼화제의 첨가량은 시멘트 고형분에 대해 0.8 중량%로 하였다.The material and concrete mix used for the test is Ssangyong Cement Co., Ltd., 365 kg of Portland cement, 891 kg of instructor, 934 kg of coarse aggregate, and 157 kg of water including cement admixture. The addition amount of each cement admixture was 0.8 weight% with respect to the cement solid content.
상기 표 1에 나타난 결과에서 알 수 있는 바와 같이, 실시예 1-5에서 제조된 본 발명 콘크리트용 혼화제를 첨가할 경우, 본 발명의 제조과정을 거치지 않은 흑액 원액를 혼화제로 사용한 콘크리트 혼합물과 비교하였을 때, 과산화수소의 양과 황산제1, 2철 및 산화방법에 관계없이 더 높은 분산성과 더 작은 슬럼프 손실, 그리고 더 높은 기계적 강도를 갖는 콘크리트를 얻을 수 있었다.As can be seen from the results shown in Table 1 above, when adding the inventive admixture for concrete prepared in Example 1-5, when compared with the concrete mixture using the black liquor stock solution that did not undergo the manufacturing process of the present invention as admixture Regardless of the amount of hydrogen peroxide, ferrous sulfate, ferric sulfate and oxidation method, concrete with higher dispersibility, smaller slump loss, and higher mechanical strength could be obtained.
이상 상기 실시예 및 제조예를 통해 설명한 바와 같이, 본 발명은 펄프 제조 시 발생된 흑액을 오존, 과산화수소, 펜톤시약 등의 산화제로 산화 처리함으로써 외부 박테리아에 의해 일어나는 부패를 방지할 수 있고, 콘크리트용 혼화제로 이용 시 굳지 않는 콘크리트의 응결지연의 원인이 되는 리그닌, 목당(-OH) 성분을 산화반응을 이용하여 알테히드(-COH), 케톤(-COR) 또는 카르복실기(-COOH)로 전환 유도하여 응결지연성이 없는 콘크리트용 혼화제로 제조할 수 있으므로 콘크리트용 혼화제 산업상 매우 유용한 발명인 것이다.As described above through the above Examples and Preparation Examples, the present invention can prevent the corruption caused by external bacteria by oxidizing the black liquor generated during the manufacture of pulp with an oxidizing agent such as ozone, hydrogen peroxide, Fenton reagent, etc. Lignin and wood sugar (-OH), which causes the coagulation delay of concrete that does not harden when used as a admixture, are converted to aldehyde (-COH), ketone (-COR) or carboxyl group (-COOH) by oxidation. The concrete admixture is very useful invention in the concrete admixture industry because it can be prepared with a concrete without adhering delay.
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| KR1020080062980A KR100963822B1 (en) | 2008-06-30 | 2008-06-30 | An admixture for concrete, prepared using black liquor from pulping process, and a method for preparation of the same |
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| KR1020080062980A KR100963822B1 (en) | 2008-06-30 | 2008-06-30 | An admixture for concrete, prepared using black liquor from pulping process, and a method for preparation of the same |
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| KR100963822B1 true KR100963822B1 (en) | 2010-06-16 |
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| FI126397B (en) | 2013-10-02 | 2016-11-15 | Teknologian Tutkimuskeskus Vtt Oy | Use of oxidized lignin as a dispersant |
| CN103755211A (en) * | 2013-12-16 | 2014-04-30 | 华南理工大学 | Papermaking black liquid modification admixture for impervious mortar and preparation method thereof |
| FI129846B (en) * | 2019-02-01 | 2022-09-30 | Andritz Oy | Method for producing oxidized lignin in kraft pulp mill |
| KR102279823B1 (en) * | 2020-10-06 | 2021-07-20 | 김광호 | Mulberry fiber pigment composition and preparation thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4764597A (en) * | 1987-06-15 | 1988-08-16 | Westvaco Corporation | Method for methylolation of lignin materials |
| KR100385580B1 (en) | 2000-03-14 | 2003-05-27 | 조성웅 | Dispersant from Lignin |
| JP2006102743A (en) * | 2004-09-07 | 2006-04-20 | Ki System:Kk | Method for black liquor treatment |
| KR20070103692A (en) * | 2006-04-19 | 2007-10-24 | 정흥호 | Compounds for concrete prepared using industrial waste and method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4764597A (en) * | 1987-06-15 | 1988-08-16 | Westvaco Corporation | Method for methylolation of lignin materials |
| KR100385580B1 (en) | 2000-03-14 | 2003-05-27 | 조성웅 | Dispersant from Lignin |
| JP2006102743A (en) * | 2004-09-07 | 2006-04-20 | Ki System:Kk | Method for black liquor treatment |
| KR20070103692A (en) * | 2006-04-19 | 2007-10-24 | 정흥호 | Compounds for concrete prepared using industrial waste and method thereof |
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