KR102657750B1 - Manufacturing Process for Cement Aid - Google Patents
Manufacturing Process for Cement Aid Download PDFInfo
- Publication number
- KR102657750B1 KR102657750B1 KR1020210156327A KR20210156327A KR102657750B1 KR 102657750 B1 KR102657750 B1 KR 102657750B1 KR 1020210156327 A KR1020210156327 A KR 1020210156327A KR 20210156327 A KR20210156327 A KR 20210156327A KR 102657750 B1 KR102657750 B1 KR 102657750B1
- Authority
- KR
- South Korea
- Prior art keywords
- limestone
- slaked lime
- sulfuric acid
- acid solution
- desulfurized gypsum
- Prior art date
Links
- 239000004568 cement Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 41
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 41
- 239000010440 gypsum Substances 0.000 claims abstract description 39
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 31
- 235000019738 Limestone Nutrition 0.000 claims abstract description 30
- 239000006028 limestone Substances 0.000 claims abstract description 30
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 27
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract 2
- 239000000178 monomer Substances 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 7
- 235000011941 Tilia x europaea Nutrition 0.000 description 7
- 239000004571 lime Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- -1 admixtures Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- 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
- C04B22/143—Calcium-sulfate
- C04B22/145—Gypsum from the desulfuration of flue gases
-
- 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
- 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
- C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
- C04B22/064—Oxides, Hydroxides of the alkali or alkaline-earth metals of the alkaline-earth metals
-
- 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
- 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
- C04B22/10—Acids or salts thereof containing carbon in the anion
-
- 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
- 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
- C04B22/141—Acids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
본 발명은 석회석과 소석회, 황산액, 탈황석고를 주재로 하여 아주 단순한 공정을 통해 양질의 시멘트 첨가제를 저비용으로 신속하게 양산할 수 있는 시멘트 첨가제 제조방법을 제공하려는 것으로서, 탈황석고와 석회석 및 소석회를 개별 사일로에 장입하는 단계(S1); 상기 석회석과 소석회를 동량으로 배합기에 투입하여 배합하는 단계 (S2), 상기 단계2를 거쳐 배합된 석회석-소석회 배합물을 1/2중량부로 소분하여 각기 중간호퍼로 옮기는 단계(S3); 각 중간호퍼의 석회석-소석회 혼합물을 1차 믹서에 투입하고, 상기 각 석회석-소석회 혼합물에 황산액을 투입 반응시키는 단계(S4) ; 상기 황산액 반응물을 2차 믹서에 투입하여 혼합하는 동시에 석회석과 소석회와 동량의 탈황석고를 각 2차 믹서에 투입하여 혼합반응시켜 배출하는 단계(S5); 로 진행하는 시멘트 첨가제 제조방법을 특징으로 한다.The present invention aims to provide a cement additive manufacturing method that can quickly mass-produce high-quality cement additives at low cost through a very simple process based on limestone, slaked lime, sulfuric acid solution, and desulfurized gypsum. Step of charging into individual silos (S1); Step (S2) of mixing the limestone and slaked lime in an equal amount into a blender; dividing the limestone-slaked lime mixture mixed through step 2 into 1/2 parts by weight and transferring them to an intermediate hopper (S3); Injecting the limestone-slaked lime mixture from each intermediate hopper into the primary mixer, and adding a sulfuric acid solution to each limestone-slaked lime mixture to react (S4); Injecting the sulfuric acid solution into a secondary mixer and mixing it, while simultaneously adding limestone, slaked lime and the same amount of desulfurized gypsum to each secondary mixer, mixing and discharging the solution (S5); It is characterized by a cement additive manufacturing method that proceeds with.
Description
본 발명은 석회석과 소석회 혼합물 황산액, 탈황석고를 주재로 하여 아주 단순한 공정을 통해 양질의 시멘트 첨가제를 저비용으로 양산할 수 있는 제조방법에 관한 것이다.The present invention relates to a manufacturing method that can mass-produce high-quality cement additives at low cost through a very simple process using limestone, slaked lime mixture, sulfuric acid solution, and desulfurized gypsum as the main ingredients.
시멘트 첨가제는 다종 다양하다. 이를테면, 아크릴산 메틸 단량체 성분 및 이와 공중합가능한 단량체 성분의 중합 반응으로 얻은 중합체로서, 상기 중합 반응의 전체 단량체 성분 중에서 아크릴산 메틸 단량체 성분의 함량이 가장 많은 중합체를 함유하는 시멘트 첨가제가 있는 가 하면,클링커 분쇄조제 또는 혼화제로 사용되는 시멘트 첨가제도 있고, 불포화 폴리알킬렌 글리콜 에테르 기재의 모노머, 말레익산 기재의 모노머 및 이들 모노머들과 공중합할 수 있는 다른 모노머로 구성되는 공중합체 또는 공중합체와 항거품제로 이뤄지는 시멘트 첨가제도 있다. There are many different types of cement additives. For example, there is a polymer obtained by the polymerization reaction of a methyl acrylate monomer component and a monomer component copolymerizable therewith, and there is a cement additive containing a polymer with the highest content of the methyl acrylate monomer component among all monomer components of the polymerization reaction, while clinker grinding There are also cement additives used as aids or admixtures, and are copolymers composed of unsaturated polyalkylene glycol ether-based monomers, maleic acid-based monomers, and other monomers that can copolymerize with these monomers, or copolymers and anti-foaming agents. There are also cement additives.
상기한 선행기술들은 복잡한 화학적 공정을 거치는 동안 첨가제의 목적 달성에 필요한 부가제, 혼화제, 분산제 등이 필요하고, 가공조건도 까다로운 데다 완제품을 얻기까지 긴 시간을 요하는 등의 이유 때문에 어느 방법으로 제조하든 시멘트 첨가제의 원가가 매우 높다. The above-mentioned prior arts require additives, admixtures, and dispersants necessary to achieve the purpose of the additive during a complex chemical process, and the processing conditions are difficult and it takes a long time to obtain the finished product, so it is manufactured by a certain method. The cost of Harden cement additives is very high.
시멘트 첨가제 중에는 탈황석고를 원료로 사용하여 제조하는 방법도 있다. 탈황석고는 황산칼슘의 농도가 높고 불순물은 적어 품질면에서 천연석고에 현저히 뒤지지 않지만, 침상 결정과 판상 결정이 혼재되어 천연석고와는 달리 수화반응에 의해 자경성을 갖지 못하기 때문에 공예품 제작, 실용적 가치가 높은 건축재용 소재로 부적합하다. 그래서 재활용 과정을 거쳐 대개 시멘트 첨가제로 사용한다. Among cement additives, there is also a method of manufacturing using desulfurized gypsum as a raw material. Desulfurized gypsum has a high concentration of calcium sulfate and low impurities, so it is not significantly inferior to natural gypsum in terms of quality, but unlike natural gypsum, it does not have self-hardening properties through hydration due to a mixture of needle-shaped crystals and plate-shaped crystals, so it has practical value for craft making. It is unsuitable as a high-density building material. Therefore, after a recycling process, it is usually used as a cement additive.
탈황석고는 SO3 42.2%, CaO 31.6%이며, SiO2, Al2O3, Fe2O3와 수분도 포함되어 있다. pH는 6.5 ~ 6.8, 용출 실험을 통하여 토양의 화학성분에 크게 영향을 미치지 않아 토양에 살포해도 생태계에 미치는 영향은 미미한 것으로 알려졌다. Desulfurized gypsum contains 42.2% SO 3 and 31.6% CaO, and also contains SiO 2 , Al 2 O 3 , Fe 2 O 3 and moisture. The pH is 6.5 to 6.8, and through dissolution experiments, it is known that it does not significantly affect the chemical composition of the soil, so even if sprayed on the soil, the impact on the ecosystem is minimal.
또, 탈황석고에서 Cr, Hg, As는 검출되지 않고, 기타 성분도 기준치보다 현저히 낮아 환경적으로 유해하지 않고, 결정구조는 CaSO4ㆍ2H2O다. In addition, Cr, Hg, and As are not detected in desulfurized gypsum, other components are significantly lower than the standard value, so it is not environmentally harmful, and the crystal structure is CaSO 4 ㆍ2H 2 O.
탈황석고는 실온에서 수분을 함유한 이수석고로 존재하고, 건조하면 수분이 제거되어 반수 또는 무수석고로 바뀐다.Desulfurized gypsum exists as dihydrate gypsum containing moisture at room temperature, and when dried, the moisture is removed and changes into semi-hydrous or anhydrous gypsum.
비철금속의 정련, 도금, 제철과 화학공업 등 여러 분야에서 폐황산액이 발생한다. 또, 반도체의 표면에 잔류하는 불순물을 황산액으로 제거하는 반도체 제조공정에서도 폐황산액이 발생하며, 반도체의 막대한 생산량에 비례하여 폐황산액도 대량으로 발생한다. Sulfuric acid waste is generated in various fields such as refining of non-ferrous metals, plating, steelmaking, and chemical industry. In addition, waste sulfuric acid liquid is also generated in the semiconductor manufacturing process in which impurities remaining on the surface of the semiconductor are removed with sulfuric acid liquid, and a large amount of waste sulfuric acid liquid is generated in proportion to the enormous production volume of semiconductors.
폐황산액은 수질, 토양의 오염원이므로 별도의 처리과정을 통해 유해성을 해소해야 한다. 폐황산액의 처리는 수산화나트륨, 탄산나트륨 등의 나트륨 화합물과 산화칼슘, 수산화칼슘, 탄산칼슘 등의 칼슘 화합물을 중화제로 중화하여 침전시키는 중화법이 유력하다. Waste sulfuric acid is a pollutant of water and soil, so its harmfulness must be eliminated through a separate treatment process. The neutralization method for treating spent sulfuric acid solution is to neutralize sodium compounds such as sodium hydroxide and sodium carbonate and calcium compounds such as calcium oxide, calcium hydroxide and calcium carbonate with a neutralizing agent to precipitate them.
폐황산액에는 중금속이 함유될 수 있으며, 그 중금속은 바륨 이온 화합물로 제거한다. Waste sulfuric acid solution may contain heavy metals, which are removed with barium ion compounds.
상기 탈황석고는 폐황산액에 석회석을 혼합하고, 탈황석고 및 석회가 혼합된 혼합물을 얻어서 탈황석고와 석회를 분리하고, 석회는 폐황산액에 석회석과 함께 투입하여 배출할 때 송풍으로 근거리에서 떨어지는 저순도 석회와 원거리에서 떨어지는 고순도 탈황석고의 분리과정을 거쳐 선별한다.The desulfurized gypsum is made by mixing limestone with a spent sulfuric acid solution, obtaining a mixture of desulfurized gypsum and lime, separating the desulfurized gypsum and lime, and the lime is added to the spent sulfuric acid solution along with limestone and falls from a short distance by blowing when discharged. It is selected through a separation process between low-purity lime and high-purity desulfurized gypsum that falls from a distance.
상기한 방법으로 얻어지는 탈황석고는 3산화황(SO3) 42 ~ 45%와 12% 이하의 수분이 함유된 기존의 탈황석고에 비해 함수율이 높고 3산화황 함유량은 적어 조기 경화가 어렵기 때문에 단독 사용은 곤란하다. 그래서 3산화황 또는 산화칼슘(CaO)을 포함하는 알칼리 자극제를 첨가하여 경화를 촉진하게 된다. 하지만, 탈황석고와 석회의 분리, 폐황산액으로 반응시킨 석회석과 석회를 송풍으로 건조하는 과정은 제조공정을 복잡하게 하고, 탈황석고와 석회 분리장치와 송풍기 추가에 따른 시설비도 가중되며, 분리장치와 송풍기의 가동에 소요되는 전기에너지 비용 부담 때문에 시멘트 첨가재로 사용되는 탈황석고의 제조원가 또한 높아 부담스럽다.The desulfurized gypsum obtained by the above method has a higher water content and lower sulfur trioxide content than the existing desulfurized gypsum, which contains 42 to 45% sulfur trioxide (SO 3 ) and less than 12% moisture, making early hardening difficult, so it must be used alone. It is difficult to use. Therefore, an alkaline stimulant containing sulfur trioxide or calcium oxide (CaO) is added to promote hardening. However, the process of separating desulfurized gypsum and lime and drying limestone and lime reacted with waste sulfuric acid solution by blowing complicates the manufacturing process, and increases facility costs due to the addition of a desulfurized gypsum and lime separation device and blower. The manufacturing cost of desulfurized gypsum used as a cement additive is also burdensome due to the burden of electrical energy costs required to operate the blower.
삭제delete
본 발명의 목적은 석회석과 소석회, 황산액, 탈황석고를 주재로 하여 아주 단순한 공정을 통해 양질의 시멘트 첨가제를 저비용으로 신속하게 양산할 수 있는 시멘트 첨가제 제조방법을 제공하는 것이다.The purpose of the present invention is to provide a cement additive manufacturing method that can quickly mass-produce high-quality cement additives at low cost through a very simple process using limestone, slaked lime, sulfuric acid solution, and desulfurized gypsum as the main ingredients.
상기 과제는, 탈황석고와 석회석 및 소석회를 1:1:1의 중량비로 각 사일로에 장입하는 단계(S1); 상기 석회석과 소석회를 동량으로 배합기에 투입하여 배합하는 단계(S2), 상기 단계2를 거쳐 배합된 석회석-소석회 배합물을 1/2중량부로 소분하여 각기 중간호퍼로 옮기는 단계(S3); 각 중간호퍼의 석회석-소석회 혼합물을 1차 믹서로 투입하고, 상기 각 석회석-소석회 혼합물에 황산액을 투입해 반응시키는 단계(S4); 상기 황산액 반응물을 2차 믹서에 투입하여 혼합하는 동시에 석회석과 소석회와 동량의 탈황석고를 각 2차 믹서에 투입하여 동반 혼합하여 반출하는 단계(S5);를 거쳐 SO3 함량 38~40중량%의 고순도 시멘트 첨가재를 제조하는 방법으로 구현할 수 있다.The above task includes charging desulfurized gypsum, limestone, and slaked lime into each silo at a weight ratio of 1:1:1 (S1); Step (S2) of mixing the limestone and slaked lime in an equal amount into a blender; dividing the limestone-slaked lime mixture mixed through step 2 into 1/2 parts by weight and transferring them to an intermediate hopper (S3); Injecting the limestone-slaked lime mixture from each intermediate hopper into the primary mixer, and adding sulfuric acid solution to each limestone-slaked lime mixture to react (S4); Adding the sulfuric acid solution reaction product to the secondary mixer and mixing it, and simultaneously adding limestone, slaked lime, and the same amount of desulfurized gypsum to each secondary mixer, mixing them, and taking them out (S5); SO 3 content of 38 to 40% by weight. It can be implemented by manufacturing high-purity cement additives.
상기 단계(S4)에서, 석회석과 소석회의 합량에 대한 황산의 주입량은 1:1.12의 중량비이다.In the step (S4), the amount of sulfuric acid injected relative to the total amount of limestone and slaked lime is a weight ratio of 1:1.12.
폐황산액과 석회석을 반응시켜 탈황석고를 얻는 과정이 배제되므로 저비용으로 시멘트 제조용 첨가제를 양산할 수 있다. 또, 최소한의 필수설비로 신속하고 효율적으로 시멘트 첨가제를 양산할 수 있다.Since the process of obtaining desulfurized gypsum by reacting waste sulfuric acid solution with limestone is eliminated, additives for cement production can be mass-produced at low cost. In addition, cement additives can be mass-produced quickly and efficiently with minimal required equipment.
도 1은 본 발명에 의한 시멘트 첨가제 제조방법의 흐름도이다.Figure 1 is a flow chart of the cement additive manufacturing method according to the present invention.
본 발명에 추구하는 시멘트 첨가제를 제조하는 기본 설비는 탈황석고 사일로(1)와 석회석 사일로(2), 소석회 사일로(3), 석회석과 소석회를 배합하는 배합기(4), 탈황석고와 석회석 배합물을 1/2중량부로 소분하여 각기 투입하는 복수의 중간 호퍼(5,6), 탈황석고를 1/2중량부로 소분하여 개별적으로 투입하는 복수의 중간 호퍼(7,8), 소분된 개별 석회석 - 소석회 배합물과 황산액을 투입하여 반응시키는 복수의 1차 믹서(9,10), 각 황산액 반응물을 투입하는 동시에 상기 각 중간 호퍼(7,8)의 탈황석고를 투입하여 혼합하는 복수의 2차 믹서(11,12)로 이뤄진다.The basic equipment for manufacturing the cement additive pursued in the present invention is a desulfurized gypsum silo (1), a limestone silo (2), a slaked lime silo (3), a blender (4) for mixing limestone and slaked lime, and a mixture of desulfurized gypsum and limestone (1). /Multiple intermediate hoppers (5,6) for dividing desulfurized gypsum into 1/2 parts by weight and individually injecting them, multiple intermediate hoppers (7,8) for dividing desulfurized gypsum into 1/2 parts by weight and individually injecting them, individual divided limestone-slaked lime mixture A plurality of primary mixers (9, 10) for injecting and reacting persulfuric acid solution, and a plurality of secondary mixers ( 11,12).
본 발명은 상기한 시멘트 첨가제 제조설비로 원하는 시멘트 첨가제를 제조하는 것이다. The present invention is to manufacture a desired cement additive using the cement additive manufacturing equipment described above.
탈황석고 사일로(1)와 석회석 사일로(2), 소석회 사일로(3)에 탈황석고(CaSO4), 석회석(CaCO3), 소석회(Ca(OH)2)를 장입한다(단계1). Desulfurized gypsum (CaSO 4 ), limestone (CaCO 3 ), and slaked lime (Ca(OH) 2 ) are charged into the desulfurized gypsum silo (1), limestone silo (2), and slaked lime silo (3) (step 1).
탈황석고와 석회석 및 소석회의 장입량은 동일한 중량비로 1:1:1을 기준으로 하고, 동량으로 자동 투하되도록 설정하여 사일로별 장입물을 수작업을 통해 개별적으로 조절하는 수고를 덜며, 정량 투입으로 양질의 시멘트 첨가제로 제조할 수 있게 한다.The charging amount of desulfurized gypsum, limestone, and slaked lime is based on the same weight ratio of 1:1:1, and is set to be automatically dispensed in the same amount, saving the trouble of individually adjusting the charge for each silo manually, and maintaining high quality quality with fixed quantity input. It can be manufactured as a cement additive.
우선, 석회석과 소석회를 1:1의 비율로 배합기(4)에 투입한다(단계2). 배합기(4)는 석회석 사일로(2)와 소석회 사일로(3)에서 각각 정량으로 투하되는 석회석과 소석회를 개별 이송 컨베이어로 동시 투입하여 일시 보관하면서 뒤섞는다.First, limestone and slaked lime are added to the mixer (4) at a ratio of 1:1 (step 2). The mixer (4) simultaneously injects limestone and slaked lime, which are dropped in fixed quantities from the limestone silo (2) and slaked lime silo (3), into individual transfer conveyors and mixes them while temporarily storing them.
배합기(4)에 배합된 석회석-소석회 배합물은 1/2중량부로 소분하여 각기 중간호퍼(5,6)를 거쳐(단계3), 1차 믹서(9,10)로 투입한 후, 각 석회석-소석회 혼합물에 황산액을 투입 반응시킨다(단계4).
이후 황산액 반응물을 2차 믹서(11,12)에 투입하여 혼합하는 동시에 석회석과 소석회와 동량의 탈황석고를 각 2차 믹서(11,12)에 투입하여 혼합반응시킨다.(단계5). 황산액의 투입량은 소분된 석회석-소석회 배합물에 대하여 1:1.12의 중량비이고, 황산액의 황산농도는 56중량% 이다.The limestone-slaked lime mixture mixed in the mixer (4) is divided into 1/2 parts by weight, passed through the intermediate hoppers (5 and 6) (step 3), and then fed into the primary mixers (9 and 10), and then each limestone-slaked lime mixture is divided into 1/2 parts by weight. Sulfuric acid solution is added to the slaked lime mixture and reacted (step 4).
Afterwards, the sulfuric acid solution is added to the secondary mixers (11 and 12) and mixed, while limestone, slaked lime and the same amount of desulfurized gypsum are added to each of the secondary mixers (11 and 12) to cause a mixing reaction (step 5). The amount of sulfuric acid solution added is a weight ratio of 1:1.12 based on the divided limestone-slaked lime mixture, and the sulfuric acid concentration of the sulfuric acid solution is 56% by weight.
삭제delete
석회석과 소석회의 황산 반응식은 아래와 같다. The reaction equation for sulfuric acid in limestone and slaked lime is as follows.
CaCO3 + H2SO4 → CaHO4 + H2CO3 CaCO 3 + H 2 SO 4 → CaHO 4 + H 2 CO 3
이 과정에서, CO2 와 H2O가 발생한다. In this process, CO 2 and H 2 O are generated.
Ca(OH)2 + H2SO4 → CaSO4 + 2H2O Ca(OH) 2 + H 2 SO 4 → CaSO 4 + 2H 2 O
상기와 같이 석회석-소석회를 황산액으로 반응시키고, 그 황산액 반응물에 탈황석고를 동량으로 배합하면 SO3 함량 40% 이상의 CaSO4과 SO3 함량 38% 이상의 CaSO4으로 된 시멘트 첨가제 CaSO4)가 얻어진다. When limestone-slaked lime is reacted with a sulfuric acid solution as described above, and an equal amount of desulfurized gypsum is mixed with the sulfuric acid solution reactant, the cement additive CaSO 4 ) consisting of CaSO 4 with an SO 3 content of 40% or more and CaSO 4 with an SO 3 content of 38% or more is produced. obtained.
이렇게 수득되는 시멘트 첨가제는 미리 수득된 탈황석고를 사용하므로 탈황석고 제조공정이 생략되어 저비용으로 신속하게 시멘트 첨가제를 제조할 수 있고, 수득된 시멘트 첨가제는 시멘트 제조공장의 시멘트 제조공정에 직투입하여 양질의 시멘트로 제조할 수 있다. The cement additive obtained in this way uses desulfurized gypsum obtained in advance, so the desulfurized gypsum manufacturing process is omitted, and the cement additive can be manufactured quickly at low cost. It can be manufactured from cement.
이상의 설명은 최적화한 설비로 석회석, 소석회, 황산액, 탈황석고를 소재로 하는 양질의 시멘트 첨가제를 제조하는 방법에 관한 것으로서, 상기한 시멘트 첨가제 제조설비를 포함하는 한 다른 구성 요소가 부가되거나 일부 구성요소를 변경 또는 등가물로 대체한 것도 광의적으론 본 발명의 기술적 범주에 속하는 것으로 봐야 한다. The above description relates to a method of manufacturing high-quality cement additives using limestone, slaked lime, sulfuric acid solution, and desulfurized gypsum using optimized equipment. As long as the above-mentioned cement additive manufacturing equipment is included, other components are added or partially formed. Changes or replacement of elements with equivalents should also be viewed as falling within the technical scope of the present invention in a broad sense.
1: 탈황석고 사일로 2: 석회석 사일로
3: 소석회 사일로 4: 배합기
5~8: 중간 호퍼 9,10: 1차 믹서
11,12; 2차 믹서 1: Desulfurized gypsum silo 2: Limestone silo
3: Slaked lime silo 4: Mixer
5~8: Middle hopper 9,10: Primary mixer
11,12; secondary mixer
Claims (2)
상기 석회석과 소석회를 동량으로 배합기에 투입하여 배합하는 단계 (S2),
상기 단계2를 거쳐 배합된 석회석-소석회 배합물을 1/2중량부로 소분하여 각기 중간호퍼로 옮기는 단계(S3);
각 중간호퍼의 석회석-소석회 혼합물을 1차 믹서에 투입하고, 상기 각 석회석-소석회 혼합물에 황산액을 투입 반응시키는 단계(S4) ;
상기 황산액 반응물을 2차 믹서에 투입하여 혼합하는 동시에 석회석과 소석회와 동량의 탈황석고를 각 2차 믹서에 투입하여 혼합반응시켜 배출하는 단계(S5); 로 진행하여 SO3 함량이 38~40중량%의 시멘트 첨가제로 제조하는 것을 특징으로 하는 시멘트 첨가제 제조방법.Step of charging desulfurized gypsum, limestone, and slaked lime into individual silos (S1);
Step (S2) of mixing the limestone and slaked lime in equal amounts into a blender,
Dividing the limestone-slaked lime mixture mixed through step 2 into 1/2 parts by weight and transferring them to an intermediate hopper (S3);
Injecting the limestone-slaked lime mixture from each intermediate hopper into the primary mixer, and adding a sulfuric acid solution to each limestone-slaked lime mixture to react (S4);
Injecting the sulfuric acid solution into a secondary mixer and mixing it, while simultaneously adding limestone, slaked lime and the same amount of desulfurized gypsum to each secondary mixer, mixing and discharging the solution (S5); A method for producing a cement additive, characterized in that the cement additive is manufactured with a SO 3 content of 38 to 40% by weight.
The method of claim 1, wherein in step 5, the sulfuric acid solution has a concentration of 56% by weight and is added at a weight ratio of 1:1.12 compared to limestone + slaked lime.
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