KR20000018843A - Manufacturing method of sulfur oxide absorbent for low temperature - Google Patents

Manufacturing method of sulfur oxide absorbent for low temperature Download PDF

Info

Publication number
KR20000018843A
KR20000018843A KR1019980036632A KR19980036632A KR20000018843A KR 20000018843 A KR20000018843 A KR 20000018843A KR 1019980036632 A KR1019980036632 A KR 1019980036632A KR 19980036632 A KR19980036632 A KR 19980036632A KR 20000018843 A KR20000018843 A KR 20000018843A
Authority
KR
South Korea
Prior art keywords
sulfur oxide
adsorbent
adsorption
low temperature
manufacturing
Prior art date
Application number
KR1019980036632A
Other languages
Korean (ko)
Other versions
KR100333184B1 (en
Inventor
임성규
김주호
마태진
Original Assignee
이호경
태경산업 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 이호경, 태경산업 주식회사 filed Critical 이호경
Priority to KR1019980036632A priority Critical patent/KR100333184B1/en
Publication of KR20000018843A publication Critical patent/KR20000018843A/en
Application granted granted Critical
Publication of KR100333184B1 publication Critical patent/KR100333184B1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

PURPOSE: A manufacturing method of a sulfur oxide absorbent for a low temperature is provided to efficiently remove sulfur oxide by increasing the reaction of an absorbing gas after oxidizing the sulfur oxide SO2 to SO3 when absorbing. CONSTITUTION: A manufacturing method of a sulfur oxide absorbent for a low temperature is comprised of the steps of: mixing more than one kind of calcium compound 15 to 80 wt %, an activator 5 to 30 wt % and white clay 5 to 20 wt % selected among hydrated lime raw lime or plastic dolomite; mixing the mixture made by adding up o.1 to 15 wt % of more than one kind selected among KMnO4, NaOH, and KOH as a catalyst in 50 to 200 wt % of water; drying at 90 to 150°C and extrusion-molding in a pallet shape by regulating the functional rate of the mixture to 10 to 30 %.

Description

저온용 황 산화물 흡착제의 제조방법Method for preparing sulfur oxide adsorbent for low temperature

본 발명은 소석회(消石灰), 생석회(生石灰), 또는 소성 돌로마이트(CaO·MgO) 등 반응성이 높은 칼슘 화합물을 주원료로 하고 여기에 활성탄, 백토와 소량의 촉매를 첨가하여 황 산화물을 함유하는 배기가스 중의 황 산화물을 흡착 제거시키는 건식, 저온용 황산화물 흡착제의 제조방법에 관한 것이다.The present invention is made from highly reactive calcium compounds such as slaked lime, quicklime, or calcined dolomite (CaO · MgO) as the main raw materials, and activated carbon, clay and a small amount of catalyst are added to exhaust gas containing sulfur oxides. It relates to a method for producing a dry, low temperature sulfur oxide adsorbent for adsorption and removal of sulfur oxides in the medium.

산업화의 발전에 따라 석탄, 석유 등 화석 연료의 사용량이 증가됨에 따라 이들 연소가스에 포함되어 있는 황 산화물(SOx), 질소 산화물(NOx) 등의 배출량도 증가하고 있으며 이들은 공기를 오염시키는 공해물질들이므로 이들에 대한 배출 규제가 점차 강화되고 있는 추세에 있다.With the development of industrialization, the use of fossil fuels such as coal and petroleum increases, and the emissions of sulfur oxides (SO x ) and nitrogen oxides (NO x ) contained in these combustion gases are also increasing. As they are substances, emission regulations for them are increasingly being tightened.

또한, 환경보호 문제는 국내적인 문제일 뿐만 아니라 지구 환경의 보호 차원에서 국제기구를 통하여 공동 대처하는 방안이 논의되고 있는 국제적인 문제이기도 하다.In addition, the issue of environmental protection is not only a domestic issue but also an international issue that discusses how to cope with international organizations in order to protect the global environment.

현재 황 산화물의 대기 방출량을 줄이는 방법으로서는 저 유황분의 연료를 사용하는 방법, 탈황된 연료를 사용하는 방법 또는 연소 후 배기 가스를 탈황(Desulfurization)하는 방법 등이 있다.Current methods for reducing the amount of sulfur oxides emitted include low sulfur fuel, desulfurized fuel, or desulfurization after combustion.

본 발명은 연소후 배기가스 탈황에 사용되는 흡착제의 제조방법에 관한 것이다.The present invention relates to a method for producing an adsorbent used for desulfurization of exhaust gases after combustion.

종래 석회와 수산화마그네슘을 이용하는 배기가스의 황 산화물 처리 방법으로는 주로 비재생(非再生) 습식 공정이 이용되고 있으나 상기의 공정은 대체로 흡착 장치에 따라 처리 성능이 좌우되기 때문에 장치 전체를 변경시키지 않으면 새로운 공정을 도입하기 어려울 뿐만 아니라, 폐수 처리 시설이 필요하고 부산물로 환경 오염의 문제가 있는 폐기물이 생성되는 등 2차적인 환경 오염 문제가 있다. 그 외에 건식 고온 탈황 공정이 일부 소규모의 보일러 등에 사용되고 있으나 경제성 및 제거 효율 등의 관점에서 문제점을 가지고 있다.Conventionally, a non-regeneration wet process is mainly used as a method for treating sulfur oxides of exhaust gas using lime and magnesium hydroxide. However, since the process performance is largely dependent on the adsorption apparatus, unless the entire apparatus is changed. Not only is it difficult to introduce new processes, but there are also secondary environmental pollution problems, such as the need for wastewater treatment facilities and the generation of waste products by-products of environmental pollution. In addition, the dry high temperature desulfurization process is used in some small boilers, but has problems in terms of economic efficiency and removal efficiency.

습식 공정에서는 슬러리(Slurry) 상태의 석회석이나 소석회, 수산화마그네슘또는 생석회를 흡수제로 하여 배기 가스중의 SO2를 CaSO3(아황산칼슘)또는 MgSO3(아황산마그네슘)으로 포집, 회수하고 이를 산화시켜 석고를 부산물로 생성한다.In the wet process, the slurry of limestone, slaked lime, magnesium hydroxide or quicklime as an absorbent is used to collect and recover SO 2 in the exhaust gas with CaSO 3 (calcium sulfite) or MgSO 3 (magnesium sulfite) and oxidize it to gypsum. To produce as a by-product.

SO2제거 공정은 다음 반응식에 따르며The SO 2 removal process is according to the following scheme

CaCO3+ SO2+ H2O → CaSO3·1/2H2O + CO2+ 1/2H2OCaCO 3 + SO 2 + H 2 O → CaSO 3 1 / 2H 2 O + CO 2 + 1 / 2H 2 O

또는 Ca(OH)2+ SO2→ CaSO3·1/2H2O + 1/2H2OOr Ca (OH) 2 + SO 2 → CaSO 3 1 / 2H 2 O + 1 / 2H 2 O

또는 Mg(OH)2+ SO2+ 5H2O→ MgSO3·6H2OOr Mg (OH) 2 + SO 2 + 5H 2 O-> MgSO 3 -6H 2 O

산화공정은 다음 반응식에 따라 진행된다.The oxidation process proceeds according to the following reaction formula.

CaSO3·1/2H2O + 1/2O2+ 3/2H2O → CaSO4·2H2OCaSO 3 1 / 2H 2 O + 1 / 2O 2 + 3 / 2H 2 O → CaSO 4 2H 2 O

또는 MgSO3+ 1/2O2→ MgSO4 Or MgSO 3 + 1 / 2O 2 → MgSO 4

석회석 슬러리 또는 석회 슬러리에 의한 SO2흡수 속도는 슬러지의 pH와 농도가 높고 흡수제의 입도가 미세할 수록 빠르다. 석회석 및 석회에 포함된 불순물이 적어야 부산물로 발생된 석고를 여과후 석고 보드 및 시멘트 첨가제용으로 사용 가능하다.The rate of SO 2 absorption by limestone slurry or lime slurry is faster as the pH and concentration of the sludge is higher and the particle size of the absorbent is finer. The less impurities contained in limestone and lime can be used for gypsum board and cement additives after filtration of gypsum generated as a by-product.

위의 반응식에서 CaCO3, Ca(OH)2,Mg(OH)2등은 수용액 중에 분산되어 있으므로 반응 생성물의 여과후 슬러지(Sludge)와 폐수가 필연적으로 발생한다.In the above scheme, since CaCO 3 , Ca (OH) 2 and Mg (OH) 2 are dispersed in an aqueous solution, sludge and waste water are inevitably generated after filtration of the reaction product.

위의 반응은 습식 반응으로써 SO2가스를 물에 용해시킨 후 슬러리 상에서 반응을 유도하는 형태의 기체-액체-고체가 함께 존재하는 일반적인 습식 처리이나 이 공정은 배출 가스 중 아황산 가스가 벌크(bulk) 상태로 존재하는 수성 슬러리와 접촉하여 흡수제와 반응을 일으키는 것으로 혼합과 접촉 시간면에서 장점은 있으나 장치가 커지고 반응 후 생성된 슬러지를 탈수하여 폐기해야 하며 또한 발생된 폐수를 정화하기 위하여 폐수 처리 설비가 필요하게 된다.The above reaction is a wet reaction, which is a general wet treatment in which a gas-liquid-solid is present in the form of dissolving SO 2 gas in water and then inducing a reaction on a slurry. Although it has advantages in terms of mixing and contact time by contacting with an aqueous slurry present in the state, it has an advantage in terms of mixing and contact time, but requires a dewatering and disposal of sludge produced after the reaction. It is necessary.

건식 배연 탈황 공정은 습식 공정에 비해 장치 규모가 비교적 작고 폐수 처리 비용이 절감되고 투자 비용이 적게 드는 대신에 SO2제거율이 낮고 고가의 흡수제 사용에 따른 장치 운전비가 많이 든다. 근본적으로 건식 배연 탈황은 기체-고체 간의 반응으로 SO2제거 효율에 한계가 있으므로 저유황 석탄 등의 연소 가스 처리에 응용한다.Dry flue gas desulfurization processes are relatively smaller in size compared to wet processes, reduce waste water treatment costs and lower investment costs, but have lower SO 2 removal rates and higher operating costs due to the use of expensive absorbents. Essentially, dry flue gas desulfurization is a gas-solid reaction, which limits the SO 2 removal efficiency and thus is applied to the treatment of combustion gases such as low sulfur coal.

건식법에서 사용되는 일반적인 금속 산화물 흡수제로는 다음 반응식과 같이 반응하는 것을 이용하는 CuO, ZnO가 있다.Common metal oxide absorbents used in the dry process include CuO and ZnO, which react by the following reaction scheme.

CuO + SO2+ 1/2O2→ CuSO4 CuO + SO 2 + 1 / 2O 2 → CuSO 4

ZnO + SO2+ 1/2O2→ ZnSO4 ZnO + SO 2 + 1 / 2O 2 → ZnSO 4

현재의 SO2제거 방법으로는 건식법과 습식법이 있는데 건식법의 단점은 CuO, ZnO 등 고가의 금속 산화물 흡수제를 사용하면서도 장치 비용 과대, SO2제거율이 낮으며, 습식법의 단점은 NaOH, Ca(OH)2,Mg(OH)2등에 의한 장치의 부식, 폐수 및 슬러지를 처리해야 하는 어려움이 발생되는데 있다. 본 발명은 이러한 건식법과 습식법의 단점을 개량한 것으로써 SO2가스를 포집하여 흡착제가 충진된 흡착탑으로 보내어 흡착하는 방식으로 장치 비용이 저렴하고 사용되는 흡착제가 저가이며, 폐수가 발생되지 않으며, 흡착이 끝난 SO2흡착제는 비재생 방식으로 매립해야 하는데 매립시 흡착제의 주성분인 석회(생석회, 소석회) 또는 소성 돌로마이트는 부수적으로 토지의 안정화 및 매립지에서 발생되는 중금속을 안정화시킴으로써 침출수에 의한 환경 오염을 방지하는 역할을 한다.Current methods of SO 2 removal include dry method and wet method. The disadvantages of dry method are the use of expensive metal oxide absorbents such as CuO and ZnO, but excessive device cost, low SO 2 removal rate, and the disadvantage of wet method is NaOH, Ca (OH). 2, Mg (OH) 2 and the like, there is a difficulty in dealing with the corrosion, waste water and sludge of the device. The present invention is to improve the shortcomings of the dry and wet method, the SO 2 gas is collected and sent to the adsorption tower filled with the adsorbent adsorption is inexpensive, the adsorbent used is low cost, no waste water generated, adsorption This SO 2 adsorbent should be landfilled in a non-regenerating manner, and lime (quick lime, hydrated lime) or calcined dolomite, which is the main component of the adsorbent, is incidentally stabilized by land stabilization and heavy metals from landfills to prevent environmental pollution by leachate. It plays a role.

본 발명은 저온 영역(120℃ 이하)에서 효과적으로 황 산화물을 제거할 수 있는 건식 흡착제의 제조방법에 관한 것이나, 본 발명의 흡착제를 이용한 탈황 공정은 황 산화물 함유 가스를 흡착제가 충진된 흡착탑으로 유입시켜 황 산화물을 흡착 제거하는 방법으로 종래의 처리공정에 비해 처리 방법이 간단하고 설비 비용이 저렴하면서 효과적으로 황 산화물을 제거할 수 있는 특징을 갖는다.The present invention relates to a method for preparing a dry adsorbent that can effectively remove sulfur oxides in a low temperature region (120 ° C. or lower), but the desulfurization process using the adsorbent of the present invention allows sulfur oxide-containing gas to flow into an adsorption tower filled with an adsorbent. As a method of adsorption and removal of sulfur oxides, the treatment method is simpler than the conventional treatment process, and the equipment cost is low, and the sulfur oxides can be effectively removed.

본 발명의 황 산화물 흡착제 제조 방법을 상세히 설명하면 다음과 같다.Hereinafter, the sulfur oxide adsorbent manufacturing method of the present invention will be described in detail.

소석회(Ca(OH)2), 생석회(CaO) 또는 소성 돌로마이트(CaO·MgO) 중에서 선택된 일종이상 15 ∼ 80wt%, 활성탄 5 ∼ 30wt%, 백토 5 ∼ 20wt%를 일정량의 물과 함께 혼합하고 여기에 촉매로서 KMnO4, NaOH, KOH 중에서 하나 이상을 선택하여 0.1 ∼ 15wt% 첨가시킨다. 혼련시 사용한 물은 전체 혼합물의 중량비에 대하여 50 ∼ 200wt%를 첨가한다. 90 ∼ 150℃의 온도에서 건조하여 혼합물의 함수율을 10 ∼ 30%로 조정한 후 압출 성형하여 펠렛트(Pellet) 형태의 황 산화물 흡착제를 제조한다.15 to 80 wt%, activated carbon 5 to 30 wt%, clay 5 to 20 wt%, selected from hydrated lime (Ca (OH) 2 ), quicklime (CaO) or calcined dolomite (CaO.MgO), are mixed with a certain amount of water At least one selected from KMnO 4 , NaOH, and KOH as a catalyst is added to 0.1-15 wt%. The water used for the kneading is added 50 to 200wt% based on the weight ratio of the entire mixture. After drying at a temperature of 90 to 150 ℃ to adjust the water content of the mixture to 10 to 30% and extrusion molding to prepare a sulfur oxide adsorbent in the form of pellets (Pellet).

이 황 산화물 흡착제에 사용되는 석회와 소성 돌로마이트는 가격이 저렴하여 쉽게 구입할 수 있을 뿐만 아니라 성형성이 양호하여 처리 방법에 따라 기공 및 비표면적을 향상시킬 수 있어서 보다 용이하게 산화물을 흡착할 수 있다.Lime and calcined dolomite used in the sulfur oxide adsorbent are inexpensive, not only easily purchased, but also have good moldability and can improve porosity and specific surface area depending on the treatment method, so that the oxide can be more easily adsorbed.

본 발명의 흡착제를 사용후 매립할 경우, 소석회는 특성상 중금속과 반응하여 수산화물을 형성하므로 침출수 내의 중금속을 효과적으로 제거할 수 있다. 생석회는 수분과 반응하여 함수율을 낮추며 매립지 내부에 존재하는 병원균을 사멸시키는 역활을 하기 때문에 쓰레기의 분해에 의한 매립지의 조기 안정화 및 매립지의 지반 강화에 도움을 준다.In the case of landfill after using the adsorbent of the present invention, hydrated lime reacts with heavy metals to form hydroxides, so that heavy metals in leachate can be effectively removed. Quicklime reacts with moisture to lower the moisture content and kills pathogens present in the landfill, thus helping to stabilize the landfill and strengthen the ground.

활성탄은 입상 및 분말 활성탄으로 구분되는데 보통 비표면적이 700∼1600m2/g 이며 유기 물질 및 중성 화합물의 탈취 성능이 우수하고 폐수 처리시 중금속 제거하는데 널리 이용된다. 본 발명에서는 가격이 저렴하고 흡착 속도가 빠른 분말 활성탄을 사용하였다.Activated carbon is divided into granular and powdered activated carbon. Its specific surface area is 700 ~ 1600m 2 / g and it is excellent in deodorizing performance of organic materials and neutral compounds and is widely used to remove heavy metals in wastewater treatment. In the present invention, powdered activated carbon having a low price and a high adsorption rate was used.

백토는 보통 탈색 및 탈취제로 널리 사용되는데 분체를 성형할 때 첨가하면 낮은 압력에서도 성형 강도를 높일 수 있는 특성이 있어서 흡착제의 충진시 압력강하의 방지에 도움을 준다.White clay is widely used as a decolorizing and deodorizing agent, and when it is added to powder, it has the property of increasing the molding strength even at low pressure, which helps to prevent the pressure drop during the filling of the adsorbent.

촉매로 사용되는 KMnO4는 일반적으로 산화제로 널리 이용되고 있으며 흡착시에 황 산화물 SO2를 SO3형태로 산화시켜 흡착 가스의 반응성을 높이므로서 황 산화물의 제거 효율을 상승시킬 수 있다.KMnO 4, which is used as a catalyst, is widely used as an oxidizing agent. In addition, sulfur oxides SO 2 are oxidized to SO 3 in adsorption to increase the reactivity of the adsorption gas, thereby increasing the removal efficiency of sulfur oxides.

한편, NaOH, KOH는 황 산화물과 중화반응에 의해 흡착성능을 향상시킬 수 있다.On the other hand, NaOH, KOH can improve the adsorption performance by the neutralization reaction with sulfur oxides.

KOH, NaOH는 흡수성이 있고 화학적으로 유사한 성질을 갖는 화합물로써 SO2와 다음 반응식에 따라 반응하며KOH and NaOH are absorbent and chemically similar compounds and react with SO 2 according to the following reaction formula.

2NaOH + SO2→ Na2SO3+ H2O2NaOH + SO 2 → Na 2 SO 3 + H 2 O

2KOH + SO2→ K2SO3+ H2O2KOH + SO 2 → K 2 SO 3 + H 2 O

Na2SO3+ SO2+ H2O → 2NaHSO3 Na 2 SO 3 + SO 2 + H 2 O → 2 NaHSO 3

K2SO3+ SO2+ H2O→ 2KHSO3 K 2 SO 3 + SO 2 + H 2 O → 2KHSO 3

발생된 NaHSO3,KHSO3는 회수 또는 폐기한다.The generated NaHSO 3 and KHSO 3 are recovered or discarded.

위의 반응에서 처럼 NaOH와 KOH는 SO2와 반응함으로써 최종 생성물은 중화 반응의 결과 각각 NaHSO3,KHSO3가 생성된다. 그러므로 SO2를 흡착 제거하기 때문에 흡착능력이 향상된다.As in the above reaction, NaOH and KOH react with SO 2 so that the end product is neutralized to produce NaHSO 3 and KHSO 3 , respectively. Therefore, the adsorption capacity is improved because SO 2 is adsorbed and removed.

촉매로 사용되는 KMnO4는 일반적으로 산화제로 널리 이용되고 있으며 흡착시에 황 산화물 SO2를 SO3형태로 신속히 산화시켜 흡착 가스의 반응성을 높이고 반응속도가 빠르게 일어나도록 함으로써 황 산화물의 제거 효율을 상승시킬 수 있다.KMnO 4 used as a catalyst is generally widely used as an oxidizing agent, and the sulfur oxide SO 2 is rapidly oxidized in the form of SO 3 at the time of adsorption to increase the reactivity of the adsorption gas and to increase the reaction rate, thereby increasing the sulfur oxide removal efficiency. You can.

활성탄 및 백토는 현재 가장 널리 사용되는 흡착제로서 비표면적이 크므로 물리 흡착의 개념으로 사용하였다. 또한 백토는 원료 중의 소석회 등이 수분 흡수력이 뛰어나므로 수분을 흡수한 펠렛트 성형체의 강도가 약해져 충진탑의 충진 시 쉽게 부서지게 된다. 이러한 문제점을 보완하기 위해 성형후 강도를 향상시킬 목적으로 사용하였다.Activated carbon and clay are currently the most widely used adsorbents and have a large specific surface area, which is used as a concept of physical adsorption. In addition, since the lime and the like in the raw material has excellent water absorption ability, the strength of the pellet molded body which absorbed moisture is weakened, so that it is easily broken during filling of the filling tower. In order to compensate this problem, it was used for the purpose of improving the strength after molding.

실시예. 1Example. One

소석회를 주원료로 하여 생석회, 활성탄, 백토, KMnO4, KOH 또는 NaOH를 물과 함께 다음 표 1에 기재한 원료 구성 비율로 혼합하여 110℃의 온도에서 함수율을 20%로 조정한 후 압출하여 펠렛트(Pellet) 형태로 성형한 황 산화물 흡착제를 제조하였다.Using lime as the main raw material, quicklime, activated carbon, clay, KMnO 4 , KOH, or NaOH is mixed with water at the raw material composition ratio shown in Table 1 below, and the water content is adjusted to 20% at a temperature of 110 ° C, followed by extrusion. A sulfur oxide adsorbent molded in the form of (Pellet) was prepared.

상기의 흡착제 600g을 칼럼에 충진하여 입구 황 산화물 농도를 10,000ppm(희석 가스 : N2), 공간 속도 200hr-1, 온도는 각각 실온, 70℃, 120℃의 조건에서 흡착 제거 실험을 실시하였다. 황 산화물 흡착능은 출구 가스에서 황 산화물 1 ppm이 검출될 때까지의 흡착 지속 시간으로 나타내었다.600 g of the above adsorbent was packed in a column, and the adsorption removal experiment was performed at conditions of inlet sulfur oxide concentration of 10,000 ppm (diluent gas: N 2 ), space velocity of 200 hr −1 , and temperature of room temperature, 70 ° C. and 120 ° C., respectively. The sulfur oxide adsorption capacity was expressed as the adsorption duration until 1 ppm of sulfur oxide was detected in the outlet gas.

표 1에는 본 실시예에서 제조한 황 산화물 흡착제의 원료비와 황 산화물 흡착 제거 결과를 나타내었다.Table 1 shows the raw material costs and sulfur oxide adsorption removal results of the sulfur oxide adsorbent prepared in this example.

본 발명의 흡착제는 특히 다음 표 1, 2 및 3에서 나타내고 있는 바와같이 실온 ∼ 120℃에서 우수한 흡착제거 성능을 나타냈다.In particular, the adsorbent of the present invention exhibited excellent adsorption and removal performance at room temperature and 120 ° C, as shown in the following Tables 1, 2 and 3.

실시예. 2Example. 2

실시예 1에서 사용한 원료 중에서 표2에 나타낸 바와같이 소석회를 소성 돌로마이트(CaO·MgO)로 대체하여 실시예 1과 같은 방법으로 제조한 황 산화물 흡착제의 흡착 제거 결과를 표 2에 나타내었다.As shown in Table 2 of the raw materials used in Example 1, the results of adsorption removal of the sulfur oxide adsorbent prepared in the same manner as in Example 1 by replacing calcined lime with calcined dolomite (CaO.MgO) are shown in Table 2.

실시예. 3Example. 3

생석회 및 기타 여러 첨가물을 혼합하기 전에 소석회를 600℃에서 1시간 동안 소성하였다. 이 때 얻어진 생석회를 물과 반응시켜 재 수화한 소석회를 주원료로 하여 실시예 1, 2와 동일한 방법으로 황 산화물 흡착제를 제조하였다. 표 3에 본 실시예에서 제조한 흡착제의 원료비와 황산화물 흡착 제거 결과를 나타내었다. 표 3에 의하면 상기의 방법으로 처리한 소석회를 사용한 흡착제가 처리하지 않은 소석회를 사용한 흡착제보다 높은 황 산화물 제거율을 나타내고 있는데 이것은 소성 및 재 수화 과정에서 소석회의 입도가 미세해지고 입도분포가 균일해져서 비표면적이 발달함에 따라 황 산화물과의 반응성이 향상되었기 때문이다.The calcined lime was calcined at 600 ° C. for 1 hour before the quicklime and various other additives were mixed. The sulfur oxide adsorbent was prepared in the same manner as in Examples 1 and 2, using the quicklime obtained by reacting the quicklime with water and rehydrated with lime. Table 3 shows the raw material cost and sulfur oxide adsorption removal results of the adsorbent prepared in this example. According to Table 3, the adsorbent using the slaked lime treated by the above method showed a higher removal rate of sulfur oxides than the adsorbent using the untreated slaked lime, which showed fine grain size and uniform particle size distribution during firing and rehydration. This is because the reactivity with sulfur oxides has been improved with this development.

실시예 1의 원료 구성비에 따른 황 산화물 흡착능Sulfur oxide adsorption capacity according to the raw material composition ratio of Example 1 실시예Example 원 료 비(%)Raw material ratio (%) 함수율(%)Moisture content (%) 황 산화물 1 ppm검출시간 (hr)Sulfur oxide 1 ppm Detection time (hr) 소석회Slaked lime 생석회quicklime 활성탄Activated carbon 백토Clay KOHKOH NaOHNaOH KMnO4 KMnO 4 실온Room temperature 70℃70 ℃ 120℃120 ℃ 1-11-1 6060 1515 1010 1010 44 ·· 1One 2020 14.614.6 13.113.1 9.49.4 1-21-2 5555 1515 1010 1010 99 ·· 1One 2020 15.015.0 13.313.3 10.010.0 1-31-3 6060 1515 1010 1010 ·· 44 1One 2020 13.913.9 10.710.7 7.47.4 1-41-4 5555 1515 1010 1010 ·· 99 1One 2020 14.914.9 12.112.1 8.68.6

실시예 2의 원료 구성비에 따른 황 산화물 흡착능Sulfur oxide adsorption capacity according to the raw material composition ratio of Example 2 실시예Example 원 료 비(%)Raw material ratio (%) 함수율(%)Moisture content (%) 황 산화물 1 ppm검출시간 (hr)Sulfur oxide 1 ppm Detection time (hr) 소성 돌로마이트Calcined dolomite 생석회quicklime 활성탄Activated carbon 백토Clay KOHKOH NaOHNaOH KMnO4 KMnO 4 실온Room temperature 70℃70 ℃ 120℃120 ℃ 2-12-1 6060 1515 1010 1010 44 ·· 1One 2525 13.113.1 12.812.8 9.09.0 2-22-2 5555 1515 1010 1010 99 ·· 1One 2525 14.614.6 13.113.1 9.69.6 2-32-3 6060 1515 1010 1010 ·· 44 1One 2525 13.013.0 10.410.4 7.17.1 2-42-4 5555 1515 1010 1010 ·· 99 1One 2525 14.114.1 12.012.0 8.08.0

실시예 3의 원료 구성비에 따른 황 산화물 흡착능Sulfur oxide adsorption capacity according to the raw material composition ratio of Example 3 실시예Example 원 료 비(%)Raw material ratio (%) 소석회소성조건Calcination firing conditions 황 산화물 1 ppm검출시간 (hr)Sulfur oxide 1 ppm Detection time (hr) 소석회Slaked lime 생석회quicklime 활성탄Activated carbon 백토Clay KOHKOH NaOHNaOH KMnO4 KMnO 4 실온Room temperature 70℃70 ℃ 120℃120 ℃ 3-13-1 6060 1515 1010 1010 44 ·· 1One 600℃, 1hr600 ℃, 1hr 15.015.0 13.613.6 10.010.0 3-23-2 5555 1515 1010 1010 99 ·· 1One 600℃, 1hr600 ℃, 1hr 15.415.4 14.114.1 10.710.7 3-33-3 6060 1515 1010 1010 ·· 44 1One 600℃, 1hr600 ℃, 1hr 14.714.7 11.511.5 8.78.7 3-43-4 5555 1515 1010 1010 ·· 99 1One 600℃, 1hr600 ℃, 1hr 15.215.2 12.512.5 9.59.5

본 발명의 흡착제를 이용한 탈황 공정은 종래의 습식처리 공정에 비해 장치가 간단하면서도 슬러지나 폐수가 발생되지 않으며 건식처리 공정에 비하여 저가의 원료를 이용하여 흡착제를 제조할 수 있으며 SO2제거 효율이 높다는 이점을 갖는다. 또한 사용 후 매립처리할 경우 중금속 등과 반응, 수산화물을 형성하므로 침출수내의 중금속을 효과적으로 제거시킬 수 있으며, 수분과 반응하여 함수율을 낮추어 주므로서 매립지의 조기안정화와 매립지의 지반 강화에도 도움을 줄 수 있는 이점이 있다.Desulfurization with the adsorbent of the present invention is that the device is simple, sludge or waste water is not generated compared to the conventional wet process to produce a sorbent using a low-cost raw material in comparison to the dry process, and high SO 2 removal efficiency Has an advantage. In addition, when the landfill treatment is used, it reacts with heavy metals and forms hydroxides, which effectively removes heavy metals in leachate and lowers water content by reacting with moisture, thereby helping to stabilize the landfill and strengthen the ground of the landfill. There is this.

Claims (2)

황 산화물 흡착제의 제조방법에 있어서, 칼슘화합물 15∼80중량%, 활성탄 5∼30중량%, 백토 5∼20중량% 혼합하고 여기에 KMnO4, NaOH, KOH 중에서 선택된 어느하나 이상을 0.1∼15중량% 첨가하여서 된 혼합물을 50∼200중량%의 물 중에서 혼련하고 90∼150℃의 온도에서 건조하여 상기 혼합물의 함수율을 10∼30%로 조정한 후 펠렛트(pellet) 형태로 압출 성형하는 저온용 황 산화물 흡착제의 제조방법.In the method for producing a sulfur oxide adsorbent, 15 to 80% by weight of calcium compound, 5 to 30% by weight of activated carbon, 5 to 20% by weight of clay is mixed, and 0.1 to 15% by weight of at least one selected from KMnO 4 , NaOH, and KOH. % Mixture was kneaded in 50 to 200% by weight of water and dried at a temperature of 90 to 150 ° C. to adjust the water content of the mixture to 10 to 30%, followed by extrusion molding into pellets. Method for producing sulfur oxide adsorbent. 제1항에 있어서, 칼슘화합물이 소석회, 생석회 또는 소성돌로마이트(CaO·MgO) 중에서 선택된 것인 저온용 황산화물 흡착제의 제조방법.The method of claim 1, wherein the calcium compound is selected from hydrated lime, quicklime or calcined dolomite (CaO.MgO).
KR1019980036632A 1998-09-05 1998-09-05 Preparing method of an absorbent for sulfur oxide in low temperature. KR100333184B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019980036632A KR100333184B1 (en) 1998-09-05 1998-09-05 Preparing method of an absorbent for sulfur oxide in low temperature.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1019980036632A KR100333184B1 (en) 1998-09-05 1998-09-05 Preparing method of an absorbent for sulfur oxide in low temperature.

Publications (2)

Publication Number Publication Date
KR20000018843A true KR20000018843A (en) 2000-04-06
KR100333184B1 KR100333184B1 (en) 2002-11-23

Family

ID=19549703

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019980036632A KR100333184B1 (en) 1998-09-05 1998-09-05 Preparing method of an absorbent for sulfur oxide in low temperature.

Country Status (1)

Country Link
KR (1) KR100333184B1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010107094A (en) * 2000-05-25 2001-12-07 유선택 Pellet type catalysts for air pollutants control
KR100835531B1 (en) * 2007-07-13 2008-06-09 허재수 Manufactruing method of doromite slurry for adsorbent of hamful gas and neutralizing agent of acid wastewater
KR20160111642A (en) 2015-03-17 2016-09-27 주식회사 자연 A cargo box equipped with the guard rail of the cargo truck
WO2016010223A3 (en) * 2014-07-17 2017-05-18 한국세라믹기술원 Desulfurizing agent for flue-gas desulfurization equipment

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101400327B1 (en) 2012-03-29 2014-05-27 현대제철 주식회사 Apparatus for recycleing activated carbon

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010107094A (en) * 2000-05-25 2001-12-07 유선택 Pellet type catalysts for air pollutants control
KR100835531B1 (en) * 2007-07-13 2008-06-09 허재수 Manufactruing method of doromite slurry for adsorbent of hamful gas and neutralizing agent of acid wastewater
WO2016010223A3 (en) * 2014-07-17 2017-05-18 한국세라믹기술원 Desulfurizing agent for flue-gas desulfurization equipment
KR20160111642A (en) 2015-03-17 2016-09-27 주식회사 자연 A cargo box equipped with the guard rail of the cargo truck

Also Published As

Publication number Publication date
KR100333184B1 (en) 2002-11-23

Similar Documents

Publication Publication Date Title
Cheng et al. Desulfurization and Denitrification Technologies of Coal-fired Flue Gas.
US5618508A (en) Process for purifying exhaust gas using modified calcium hydroxide
US4859438A (en) Method for separation of impurities from flowing gas
EP0613397B1 (en) A METHOD OF IMPROVING THE Hg-REMOVING CAPABILITY OF A FLUE GAS CLEANING PROCESS
US5173279A (en) Method and composition for treating flue or exhaust gases utilizing modified calcium hydroxide
US7771700B2 (en) Sorbents for removal of mercury from flue gas cross reference to related applications
CA2714140C (en) Air pollution reduction solution
US20070092418A1 (en) Sorbents for Removal of Mercury from Flue Gas
US5635150A (en) Sorption of acidic gases by solid residue from sugar refining
WO2017019283A1 (en) Sulfur enhanced nitrogen production from emission scrubbing
CA2704526C (en) A method for stabilization and/or fixation of leachable metals
US3855391A (en) Sludge stabilization with gypsum
US20100145130A1 (en) Treatment Method for Stabilizing Selenium in Coal Combustion Ash
KR101099073B1 (en) Composition for removing sox in exhausted gas
KR100333184B1 (en) Preparing method of an absorbent for sulfur oxide in low temperature.
CA2904381C (en) Use of ferrous sulfide suspension for the removal of mercury from flue gases
KR100888336B1 (en) A desulfurizing sorbent for so2 removal and a process for the preparation thereof
KR100342696B1 (en) Ca-based absorbent for acid gas treatment and method for preparing the same
KR101139017B1 (en) Absorbent for treatment of hazardous gas and preparing method thereof and treating method of hazardous gas using thereof
CN111701437A (en) Flue gas desulfurizing agent
JP2000051645A (en) Method for treating exhaust gas and fly ash
JP2000051658A (en) Incinerator flue blown agent and exhaust gas treatment method
CN113996176B (en) Efficient heating furnace flue gas desulfurizing agent and preparation method and application thereof
Zhang et al. Preparation and characterization of a new desulfurizer and its performance on removal of SO2
RU2684088C1 (en) Method of cleaning the flue gases of thermal devices from toxic compounds

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E902 Notification of reason for refusal
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20130404

Year of fee payment: 12

FPAY Annual fee payment

Payment date: 20140407

Year of fee payment: 13

FPAY Annual fee payment

Payment date: 20160406

Year of fee payment: 15

LAPS Lapse due to unpaid annual fee