KR20180077859A - Adsorbent with excellent formability and preparation method thereof - Google Patents

Adsorbent with excellent formability and preparation method thereof Download PDF

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KR20180077859A
KR20180077859A KR1020160182648A KR20160182648A KR20180077859A KR 20180077859 A KR20180077859 A KR 20180077859A KR 1020160182648 A KR1020160182648 A KR 1020160182648A KR 20160182648 A KR20160182648 A KR 20160182648A KR 20180077859 A KR20180077859 A KR 20180077859A
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precipitate
adsorbent
ammonia water
mixture
silica gel
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KR1020160182648A
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Korean (ko)
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김신동
박성순
서영주
박준우
박현영
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주식회사 이앤켐솔루션
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Priority to KR1020160182648A priority Critical patent/KR20180077859A/en
Priority to PCT/KR2017/002037 priority patent/WO2018124384A1/en
Publication of KR20180077859A publication Critical patent/KR20180077859A/en

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    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0259—Compounds of N, P, As, Sb, Bi
    • 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
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • 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
    • 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
    • B01J20/3071—Washing or leaching
    • 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
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing

Abstract

The present invention relates to an adsorbent excellent in formability, capable of removing hydrogen sulfide, siloxane, etc. with high efficiency by using fumed silica or silica gel, ammonia water, and a poly-ferric sulfate solution; and a production method thereof. According to the present invention, the production method of the adsorbent excellent in formability comprises: a step of mixing fumed silica, silica gel, or a mixture thereof with ammonia water at a weight ratio of 1:20 to 1:60 and stirring poly-ferric sulfate until the pH of the mixture reaches 6 to 9 to produce a precipitate; a step of separating the solid phase precipitate and liquid contained in the mixture; a step of washing the precipitate with washing water; and a step of drying the precipitate.

Description

성형성이 우수한 흡착제 및 이의 제조방법{Adsorbent with excellent formability and preparation method thereof}[0001] The present invention relates to an adsorbent having excellent formability and an adsorbent having excellent formability and preparation method thereof,

본 발명은 흄드 실리카 또는 실리카겔과, 암모니아수 및 폴리황산철 용액을 이용하여 황화수소, 실록산 등을 고효율로 제거할 수 있는 성형성이 우수한 흡착제 및 이의 제조방법에 관한 것이다.The present invention relates to an adsorbent excellent in moldability and capable of removing hydrogen sulfide, siloxane, and the like with high efficiency using fumed silica or silica gel, aqueous ammonia solution, and an aqueous solution of polyphosphorus, and a method for producing the same.

산업의 발전과 경제규모의 팽창에 따라 에너지소비가 크게 증가되는 가운데 대기오염물질배출이 크게 늘어나면서 심각한 환경문제를 야기하고 있다. 이중에서 황화수소(H2S)는 계란 썩는 냄새가 나는 무색의 유독한 기체로서 인체의 위장이나 폐에 흡수되어 질식, 폐 질환, 신경중추마비 등을 발생시키고 있다. H2S 가스는 폐기물 매립장, 석유 정제업, 펄프공업, 도시가스 제조업, 암모니아공업, 하수처리장 등 다양한 곳에서 발생하고 있으며, 이를 처리하기 위하여 심냉법, 흡수법, 막분리법, 흡착법 등 여러 가지 처리 방법이 제시되어 있으며, 주로 흡착법이 많이 적용되고 있다. With the development of industry and the expansion of economic scale, energy consumption is greatly increased and air pollutant emissions are increasing so that it causes serious environmental problems. Among them, hydrogen sulfide (H2S) is a colorless, toxic gas that smells of eggs and is absorbed into the stomach or lungs of the human body, resulting in phos- phorus, lung disease, and nerve palsy. H2S gas is generated in various places such as waste landfill, oil refining industry, pulp industry, city gas manufacturing, ammonia industry, sewage treatment plant and various treatment methods such as seawater cooling method, absorption method, membrane separation method and absorption method are presented And the adsorption method is mainly applied.

기존의 흡착제로 많이 사용되는 활성탄은 높은 기계적 강도, 넓은 비표면적을 가진 고체로 악취물질을 분자 간 인력이나 정전기력으로 표면에 흡착시켜 제거하는데 큰 역할을 해왔으며, 산업적으로 많이 적용되고 있다. 그러나, 활성탄은 흡착효율이 낮고, 흡착제의 충전량이 많으며, 시설의 용량이 크고, 시설비의 투자가 높아 경제적인 측면에서 가격이 비싼 문제가 있다.Activated carbon, which is widely used as a conventional adsorbent, has a high mechanical strength and a wide specific surface area, and has played a large role in adsorbing and removing odorous substances on the surface by intermolecular force or electrostatic force, and is widely applied in industry. However, there is a problem in that the activated carbon has a high adsorption efficiency, a large charge amount of the adsorbent, a large capacity of the facility, and a high investment cost of the facility.

대한민국공개특허번호 제10-2015-0016624 (공개일:2015.02.12)Korean Patent Publication No. 10-2015-0016624 (Publication date: 2015.02.12)

본 발명이 해결하고자 하는 과제는 흄드 실리카 또는 실리카겔과, 암모니아수 및 폴리황산철 용액을 이용하여 황화수소, 실록산 등을 고효율로 제거할 수 있는 성형성이 우수한 흡착제 및 이의 제조방법에 관한 것이다.An object of the present invention is to provide an adsorbent excellent in moldability capable of removing hydrogen sulfide, siloxane, and the like with high efficiency using fumed silica or silica gel, ammonia water, and an aqueous solution of polypheny solution, and a method for producing the same.

본 발명에 따른 성형성이 우수한 흡착제는 흄드 실리카, 실리카겔 또는 이들의 혼합물과, 암모니아수 및 폴리황산철이 혼합되어 고상으로 침전된 침전물인 것을 특징으로 한다.The adsorbent excellent in moldability according to the present invention is characterized in that it is a precipitate mixed with fumed silica, silica gel or a mixture thereof, ammonia water and polysulfate and precipitated in a solid phase.

바람직하게, 흄드 실리카, 실리카겔 또는 이들의 혼합물과 암모니아수는 1 : 20 내지 1 : 60의 중량비로 사용되고, 폴리황산철을 pH가 6~10이 되도록 첨가되는 것을 특징으로 한다.Preferably, the fumed silica, silica gel or mixture thereof and ammonia water are used in a weight ratio of 1:20 to 1:60, and the polysulfate is added so as to have a pH of 6 to 10.

바람직하게, 암모니아수의 농도는 6~20중량%인 것을 특징으로 한다.Preferably, the concentration of ammonia water is from 6 to 20% by weight.

바람직하게, 폴리황산철은 2 내지 15중량%의 철이온을 함유하는 것을 특징으로 한다.Preferably, the polysulfide iron is characterized by containing from 2 to 15% by weight of iron ions.

본 발명에 따른 성형성이 우수한 흡착제의 제조방법은, 흄드 실리카, 실리카겔 또는 이들의 혼합물과 암모니아수를 1 : 20 내지 1 : 60의 중량비로 혼합하면서 혼합액의 pH가 6~9에 도달될 때까지 폴리황산철을 적정하면서 교반하여 침전물을 생성하는 단계와; 혼합물에 포함된 고상의 침전물과 액체를 분리하는 단계와; 침전물을 세정수로 세척하는 단계 및 침전물을 건조하는 단계를 포함하는 것을 특징으로 한다.The method for producing an adsorbent excellent in moldability according to the present invention is a method for producing an adsorbent excellent in moldability, comprising mixing fumed silica, silica gel or a mixture thereof with ammonia water at a weight ratio of 1:20 to 1:60, Stirring the iron sulfate with an appropriate amount to produce a precipitate; Separating the solid phase precipitate and liquid contained in the mixture; Washing the precipitate with washing water, and drying the precipitate.

바람직하게, 건조단계 이후에 분말 또는 펠렛으로 성형하는 압출성형단계를 더 포함하는 것을 특징으로 한다.Preferably, the method further comprises an extrusion step of molding into a powder or pellet after the drying step.

바람직하게, 건조단계는 100℃이상에서 건조하여 수분함량을 30중량% 이하인 것을 특징으로 한다.Preferably, the drying step is performed at a temperature of 100 ° C. or higher to have a water content of 30% by weight or less.

본 발명에 따른 흡착제는 일반적으로 수산화철을 분말로 제조하기 때문에 일정한 형상의 모양으로 성형하기 위해서는 바인더(성형제)를 사용해야 하지만 자체 바인딩 능력(성형성)을 가지고 있기 때문에 바인더를 사용할 필요가 없을 뿐아니라 바인더에 의한 기공 막힘 현상도 회피할 수 있어서 매우 높은 흡착능을 갖는다. 이는 경제적으로 매우 큰 장점을 갖는다.Since the adsorbent according to the present invention generally comprises iron hydroxide as a powder, it is necessary to use a binder (molding agent) for shaping into a certain shape, but since it has its own binding ability (moldability), it is not necessary to use a binder It is possible to avoid the phenomenon of pore clogging due to the binder, and thus has a very high adsorption capacity. This is very economically advantageous.

본 발명의 흡착제는 황화수소의 제거율은 99%이상을 나타내었고, 황화수소 흡착능이 무게비로 25%를 상회하는 매우 우수한 흡착특성을 갖는 장점이 있다.The adsorbent of the present invention exhibits a hydrogen sulfide removal rate of 99% or more, and has an excellent adsorption property with a hydrogen sulfide adsorbing ability exceeding 25% by weight.

본 발명의 흡착제는 실록산의 게거율도 99% 이상의 높은 흡착특성을 갖는 장점이 있다.The adsorbent of the present invention is advantageous in that the siloxane has a high adsorption characteristic of 99% or more.

도 1은 본 발명에 따른 성형성이 우수한 흡착제을 이용한 흡착탑에서 배출되는 황화수소의 흡착능 그래프(파과곡선).
도 2는 본 발명의 흡착제가 설치된 탈황장치에서 배출되는 황화수소, 실록산의 흡착결과를 나타낸 실험성적서.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph of adsorption capability (breakthrough curve) of hydrogen sulfide discharged from an adsorption tower using an adsorbent excellent in moldability according to the present invention. FIG.
2 is an experimental report showing adsorption results of hydrogen sulfide and siloxane discharged from a desulfurizer equipped with an adsorbent of the present invention.

이하 본 발명을 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명에 따른 성형성이 우수한 흡착제는 흄드 실리카, 실리카겔 또는 이들의 혼합물, 암모니아수 및 폴리황산철을 혼합하여 교반하고 생성된 침전물을 건조되켜 생성된다.The adsorbent having excellent moldability according to the present invention is produced by mixing and stirring fumed silica, silica gel or a mixture thereof, ammonia water and iron polysulfate, and drying the resulting precipitate.

즉, 본 발명에 따른 황화수소 제거용 흡착제의 제조방법은 흄드 실리카, 실리카겔 또는 이들의 혼합물과 암모니아수를 1 : 20 내지 1 : 60의 중량비로 혼합하면서 혼합액의 pH가 6~9, 바람직하게 pH가 7.5~8.5에 도달될 때까지 폴리황산철을 서서히 적정하면서 교반하여 침전물을 생성하는 단계와, 침전물을 세척수로 수차례 세척하는 단계 및 침전물을 건조하는 단계로 이루어진다. 필요에 따라, 건조 단계 이후에 흡착제의 사용형태에 따라 분말, 펠렛 등으로 성형하는 압출성형단계를 더 구비할 수 있다.That is, in the method of preparing the adsorbent for removing hydrogen sulfide according to the present invention, the pH of the mixed solution is adjusted to 6 to 9, preferably the pH is adjusted to 7.5, by mixing the fumed silica, silica gel or a mixture thereof with ammonia water at a weight ratio of 1:20 to 1:60. Stirring the titanyl polysulfate slowly until titration is reached to produce a precipitate, washing the precipitate several times with wash water, and drying the precipitate. If necessary, it may further comprise an extrusion molding step of molding the powder into powder, pellets or the like according to the use form of the adsorbent after the drying step.

본 발명의 흄드 실리카 또는 실리카겔은 이산화규소와 알칼리를 융해해서 얻은 규산알칼리염으로부터 알칼리염을 제거한 물질로, 백색이나 회백색에 이르는 다양한 색을 가진 분말이다. 이러한 흄드 실리카 또는 실리카겔는 단독으로 사용할 수 있지만, 이들을 혼합하여 사용할 수도 있다. 흄드 실리카 또는 실리카겔 99% 이상의 순도를 갖는 것이 바람직하다.The fumed silica or silica gel of the present invention is a material in which an alkali salt is removed from an alkali silicate obtained by melting silicon dioxide and alkali, and has various colors ranging from white to off-white. These fumed silica or silica gel may be used alone, but they may be mixed and used. Fumed silica or silica gel having a purity of 99% or more.

암모니아수는 황산이온과 반응하여 황산암모늄 염이온을 형성한다. 이러한 암모니아수는 폴리황산철을 산화시켜 수산화철을 형성하게 된다. 암모니아수를 사용하면 다른 알카리 용액보다 세척이 용이하여 높은 비표면적의 흡착제를 제조하는 것이 가능하고, 세척수에 포함된 암모니아를 적당한 공정을 통하여 암모니아수로 다시 재생하여 사용하는 것이 가능하다. 본 발명은 2~28중량%의 농도, 바람직하게는 6~20중량%를 갖는 암모니아수를 사용하는 것이 바람직하다. 고농도의 암모니아는 중화 공정이 어렵고, 증발하는 암모니아의 위해성이 큰 문제가 있다.Ammonia water reacts with sulfate ions to form ammonium sulfate ion. The ammonia water oxidizes the poly-sulfate to form iron hydroxide. When ammonia water is used, it is possible to produce an adsorbent having a high specific surface area because it is easier to wash than other alkaline solutions, and it is possible to regenerate ammonia contained in the washing water through ammonia water again through an appropriate process. The present invention preferably uses ammonia water having a concentration of 2 to 28% by weight, preferably 6 to 20% by weight. The high concentration of ammonia has a problem in that the neutralization process is difficult and the risk of ammonia evaporating is large.

그리고, 폴리황산철(황산이철)은 철화합물이 반복적으로 중합되어 형성된 고분자 물질이며 사슬모양 또는 그물모양 구조를 가지고 있다. 이러한 폴리황산철은 흄드 실리카 또는 실리카겔과 암모니아수의 혼합액에 첨가되면서 산화되어 사슬 또는 그물 구조의 형태를 갖게 되어 비표면적이 높은 수산화철로 변하게 된다. 이때, 폴리황산철은 2 내지 15중량%의 철이온을 함유하고, 바람직하게는 5~11중량%의 철이온을 함유하는 것이다.Poly (ferric sulfate) is a polymer substance formed by repeatedly polymerizing iron compounds and has a chain-like or net-like structure. These poly (ferric sulfate) are added to the mixture of fumed silica or silica gel and ammonia water to be oxidized to form a chain or net structure, thereby changing to iron hydroxide having a high specific surface area. At this time, the iron polysulfate contains 2 to 15% by weight of iron ions, preferably 5 to 11% by weight of iron ions.

흄드 실리카, 실리카겔 또는 이들의 혼합물, 암모니아수 및 폴리황산철은 동시에 혼합하여 교반하거나 또는 순차적으로 혼합하여 교반한다. 이때, 흄드 실리카, 실리카겔 또는 이들의 혼합물과 암모니아수의 혼합비율은 1 : 20 내지 1 : 60의 중량비로 혼합되고, 폴리황산철은 혼합액의 pH가 6~9, 바람직하게는 pH 7.5~8.5가 되도록 투입하여 중화 적정으로 침전물을 생성하다. Fumed silica, silica gel or a mixture thereof, ammonia water and ferrous polysulfate are mixed at the same time and stirred or sequentially mixed and stirred. At this time, the mixing ratio of the fumed silica, the silica gel or the mixture thereof and the ammonia water is mixed at a weight ratio of 1:20 to 1:60, and the pH of the mixed solution is 6 to 9, preferably 7.5 to 8.5 And the precipitate is formed by neutralization titration.

이때, 암모니아수가 20 중량비 이하이면 흡착제에서 흡착역할을 하는 수산화철의 비율이 작아지므로 흡착성능이 감소하고, 60 중량비 이상이면 흡착물질에서 수산화철 비율이 증가하여 지지체 역할을 하는 SiO2의 비율이 감소하므로 물리적 강도가 감소하는 단점이 있다. 또한, 혼합액이 경우에도 pH가 6 미만이면 침전이 일어나기 어렵고, 수율이 저하되는 단점이 있고, pH 9 초과이면 흡착능이 서서히 감소하는 단점이 있다. 폴리황산철을 사용하면 폴리황산철에 포함된 SO4 2-(황산이온)은 암모니아수에 포함된 NH4+ 이온과 용해도가 매우 큰 염((NH4)2SO4)을 생성되지만, 생성된 염은 세척수로 수차례 세척하여 쉽게 제거할 수 있다. 제거가 되지 않으면, 흡착제의 성능이 확연하게 감소한다. In this case, since ammonia is 20 weight ratio or less it is because the ratio of iron hydroxide decreases to the suction part in an adsorbent decreases the suction performance, and increased iron hydroxide ratio at the back adsorbent material more than 60 weight ratio to decrease the ratio of SiO 2 to a support role physical There is a drawback that strength is reduced. In addition, even in the case of the mixed solution, if the pH is less than 6, precipitation hardly occurs and the yield is lowered. On the other hand, when the pH is more than 9, the adsorbing ability is gradually decreased. When using polysulfated iron, SO 4 2- (sulfate ion) contained in the polysulfate produces NH 4 + ions contained in ammonia water and salts ((NH 4 ) 2 SO 4 ) having a very high solubility, Salts can be easily removed by washing several times with wash water. If not removed, the performance of the adsorbent is significantly reduced.

또한, 흄드실리카 또는 실리카겔, 암모니아수 및 폴리황산철로 생성된 침전물을 100℃이상에서 건조하여 수분함량을 30중량%이하로 유지하는 것이 바람직하다. 이때, 침전물을 250℃ 이상의 온도에서 건조시킬 경우에는 제조되는 수산화철의 구조가 비정질에서 결정질 형태로 전환되어 비표면적이 감소되기 때문에 250℃ 이하에서 건조하는 것이 바람직하다. In addition, it is preferable to dry the precipitate formed from fumed silica or silica gel, ammonia water and polysulfated iron at 100 DEG C or higher to maintain the water content at 30 wt% or less. At this time, when the precipitate is dried at a temperature of 250 ° C or higher, the structure of iron hydroxide to be produced is converted from amorphous to crystalline form, and the specific surface area is reduced.

<실시예1>&Lt; Example 1 >

10중량%의 농도를 갖는 암모니아수 600g에 흄드 실리카 10g을 혼합한 후 11중량%의 철이온 농도를 갖는 폴리황산철 수용액 600g을 혼합하면서 교반하여 침전물을 생성하고, 증류수로 충분히 세척하였다. 그 후, 얻어진 케익(페이스트)을 150℃로 건조시킨 후에 한 후에 얻어진 케익(페이스트)을 건조기에서 건조하여 흡착제로 성형하였다.10 g of fumed silica was mixed with 600 g of ammonia water having a concentration of 10% by weight, and 600 g of an aqueous solution of iron polysulfate having an iron ion concentration of 11% by weight was mixed with stirring to produce a precipitate and sufficiently washed with distilled water. Thereafter, the resulting cake (paste) was dried at 150 DEG C, and then the obtained cake (paste) was dried in a drier and formed into an adsorbent.

<실시예2>&Lt; Example 2 >

10중량%의 농도를 갖는 암모니아수 600g에 실리카겔 30.5g을 혼합한 후 11중량%의 철이온 농도를 갖는 폴리황산철 수용액 600g을 혼합하면서 교반하여 침전물을 생성하고, 증류수로 충분히 세척하였다. 그 후, 얻어진 케익(페이스트)을 150℃로 건조시킨 후에 한 후에 얻어진 케익(페이스트)을 건조기에서 건조하여 흡착제로 성형하였다.600g of ammonia water having a concentration of 10% by weight was mixed with 30.5g of silica gel, and 600g of an aqueous solution of iron polysulfate having an iron ion concentration of 11% by weight was mixed with stirring to produce a precipitate and sufficiently washed with distilled water. Thereafter, the resulting cake (paste) was dried at 150 DEG C, and then the obtained cake (paste) was dried in a drier and formed into an adsorbent.

<실험예1><Experimental Example 1>

실시예1, 실시예2에서 흡착제의 기공특성을 확인하여 표 1에 나타내었다.Table 1 shows the pore characteristics of the adsorbent in Examples 1 and 2.

구 분division 실시예1Example 1 실시예2Example 2 비표면적 (m2/g)Specific surface area (m 2 / g) 225225 264264 총 세공용적 (cm2/g)Total pore volume (cm 2 / g) 0.280.28 0.320.32 평균세공직경 (Å)Average pore diameter (Å) 50.550.5 48.548.5

표 1에 나타난 바와 같이, 실시예1 및 실시예2의 흡착제는 황화수소, 실록산 등과 접촉하면서 흡수할 수 있는 세공이 형성된 것을 확인할 수 있었다.As shown in Table 1, it was confirmed that the adsorbents of Examples 1 and 2 formed pores capable of absorbing while being in contact with hydrogen sulfide, siloxane and the like.

<실험예2><Experimental Example 2>

실시예1 또는 실시예2에서 제조된 흡착제 2.5g를 4.7ml의 건식 흡착탑에 설치하고 황화수소가 포함된 가스를 통과시켜 황화수소 제거율을 확인하여 도 1의 그래프로 나타내었다. 실험조건은 초기 황화수소 농도는 3,000ppm이고, 공간속도(Space Velocity, hr-1)는 1,000hr-1이었다. 2.5 g of the adsorbent prepared in Example 1 or Example 2 was placed in a 4.7 ml dry adsorption tower and a hydrogen sulfide-containing gas was passed therethrough to confirm the hydrogen sulfide removal rate. The experimental conditions and the initial hydrogen sulfide concentration of 3,000ppm, space velocity (Space Velocity, hr -1) was 1,000hr -1.

도 1의 그래프에서 확인할 수 있듯이 실시예1 및 실시예2의 흡착제는 약 13시간이 경과될 때까지 흡착탑으로 유입된 가스에 포함된 거의 모든 황화수소가 흡착되어 황화수소(H2S)의 제거율이 99.9% 이상인 우수한 흡착성능을 갖는 것을 확인할 수 있었으며, 황화수소 파과흡착능도 27wt%임을 확인할 수 있었다.As can be seen from the graph of FIG. 1, almost all the hydrogen sulfide contained in the gas introduced into the adsorption tower was adsorbed until the removal of hydrogen sulfide (H 2 S) was 99.9 %, And it was confirmed that the adsorption capacity of hydrogen sulfide was 27wt%.

<실험예3><Experimental Example 3>

실시예1에서 제조된 흡착제를 탈황장치에 설치하고 황화수소, 실록산이 포함된 가스를 통과시켜 검출여부를 확인하여 도 2에 나타내었다.The adsorbent prepared in Example 1 was installed in a desulfurizer, and a gas containing hydrogen sulfide and siloxane was passed to check whether or not the adsorbent was detected.

도 2의 시험결과에서 확인할 수 있듯이, 황화수소의 경우에 1439 ppm이 유입되더라도 99.9% 흡착할 수 있는 것을 확인할 수 있으며, 실록산의 경우에도 0.06 mg/㎥ 이더라도 모두 흡착할 수 있는 것을 확인할 수 있다.As can be seen from the test results in FIG. 2, it can be confirmed that even when 1439 ppm is introduced in the case of hydrogen sulfide, 99.9% can be adsorbed. Even in the case of siloxane, it can be adsorbed even if 0.06 mg / m 3.

이상과 같이, 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 이것에 의해 한정되지 않으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 본 발명의 기술사상과 아래에 기재될 청구범위의 균등범위 내에서 다양한 수정 및 변형이 가능함은 물론이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Various modifications and variations are possible within the scope of the appended claims.

Claims (9)

흄드 실리카, 실리카겔 또는 이들의 혼합물과, 암모니아수 및 폴리황산철이 혼합되어 고상으로 침전된 침전물인 것을 특징으로 하는 성형성이 우수한 흡착제.
Wherein the adsorbent is a precipitate obtained by mixing fumed silica, silica gel or a mixture thereof with ammonia water and polysulfate and precipitating in a solid phase.
청구항 1에 있어서, 흄드 실리카, 실리카겔 또는 이들의 혼합물과 암모니아수는 1 : 20 내지 1 : 60의 중량비로 사용되고, 폴리황산철을 pH가 6~10이 되도록 첨가되는 것을 특징으로 하는 성형성이 우수한 흡착제.
The adsorbent according to claim 1, wherein the fumed silica, silica gel or a mixture thereof and ammonia water are used in a weight ratio of 1:20 to 1:60, and the pH is 6 to 10, .
청구항 1에 있어서, 암모니아수의 농도는 6~20중량%인 것을 특징으로 하는 성형성이 우수한 흡착제.
The adsorbent according to claim 1, wherein the concentration of ammonia water is from 6 to 20% by weight.
청구항 1에 있어서, 폴리황산철은 2~15중량%의 철이온을 함유하고 있는 것을 특징으로 하는 성형성이 우수한 흡착제.
The adsorbent according to claim 1, wherein the polyphosphoric acid iron contains 2 to 15% by weight of iron ions.
흄드 실리카, 실리카겔 또는 이들의 혼합물과 암모니아수를 1 : 20 내지 1 : 60의 중량비로 혼합하면서 혼합액의 pH가 6~9에 도달될 때까지 폴리황산철을 적정하면서 교반하여 침전물을 생성하는 단계와,
혼합물에 포함된 고상의 침전물과 액체를 분리하는 단계와;
침전물을 세정수로 세척하는 단계 및
침전물을 건조하는 단계를 포함하는 것을 특징으로 하는 성형성이 우수한 흡착제 제조방법.
Mixing ammonium fumed silica, silica gel or a mixture thereof with ammonia water at a weight ratio of 1:20 to 1:60, stirring the titurated polysulfate until the pH of the mixture reaches 6 to 9 to produce a precipitate,
Separating the solid phase precipitate and liquid contained in the mixture;
Washing the precipitate with washing water and
And drying the precipitate. The adsorbent according to claim 1,
청구항 5에 있어서, 건조단계 이후에 분말 또는 펠렛으로 성형하는 압출성형단계를 더 포함하는 것을 특징으로 하는 성형성이 우수한 흡착제 제조방법..
The method of claim 5, further comprising the step of extruding the powder or pellet after the drying step.
청구항 5에 있어서, 암모니아수의 농도는 6~20중량%인 것을 특징으로 하는 성형성이 우수한 흡착제 제조방법.
The method of claim 5, wherein the concentration of ammonia water is 6 to 20 wt%.
청구항 5에 있어서, 폴리황산철은 2~15중량%의 철이온을 함유하고 있는 것을 특징으로 하는 성형성이 우수한 흡착제 제조방법.
The method for producing an adsorbent according to claim 5, wherein the iron polysulfate contains 2 to 15% by weight of iron ions.
청구항 5에 있어서, 건조 단계는 침전물의 수분함량이 30중량%이하로 건조시키는 것을 특징으로 하는 성형성이 우수한 흡착제 제조방법.[6] The method of claim 5, wherein the drying step comprises drying the water content of the precipitate to 30 wt% or less.
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