KR102478521B1 - Composite adsorbent containing coffee beans and iron hydroxide - Google Patents

Composite adsorbent containing coffee beans and iron hydroxide Download PDF

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KR102478521B1
KR102478521B1 KR1020220107326A KR20220107326A KR102478521B1 KR 102478521 B1 KR102478521 B1 KR 102478521B1 KR 1020220107326 A KR1020220107326 A KR 1020220107326A KR 20220107326 A KR20220107326 A KR 20220107326A KR 102478521 B1 KR102478521 B1 KR 102478521B1
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waste
coffee
activated carbon
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박시진
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가야활성탄소(주)
박시진
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
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    • 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
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    • 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
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • 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
    • B01D2257/304—Hydrogen sulfide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The present invention provides a composite adsorbent for purifying acidic and alkaline odors containing activated carbon from coffee waste. The composite adsorbent according to the present invention can remove acidic gas such as hydrogen sulfide and alkaline gas such as ammonia included in odorous gas, and at the same time, has no exothermic reaction with oxygen, and shows excellent removal performance.

Description

커피박과 수산화철이 함유된 복합 흡착제{Composite adsorbent containing coffee beans and iron hydroxide}Composite adsorbent containing coffee beans and iron hydroxide}

본 발명은 커피박과 수산화철이 함유된 복합 흡착제에 관한 것으로, 상세하게는 산성 및 알칼리성 악취 정화가 가능한 복합 흡착제에 관한 것이다.The present invention relates to a composite adsorbent containing coffee grounds and iron hydroxide, and more particularly, to a composite adsorbent capable of purifying acidic and alkaline odors.

많은 산업설비, 특히 제조업분야, 축산업 분야 등에서는 각종 유독성 악취가 방출되고 있으며, 이러한 악취는 불쾌함, 구토 및 두통 등 인체에 직접적으로 해를 끼치거나, 대기오염 등의 환경오염을 유발하는 문제를 갖고 있다. 특히 이러한 악취로는 각종 고압가스 혼합장치, 분석기기 및 화학공장 등에서 자주 발생하는 황화수소, 메르카탄 등을 포함하는 산성가스와 암모니아, 아민류가스 등을 포함하는 알칼리성가스를 들 수 있다.Various toxic odors are emitted from many industrial facilities, especially in the manufacturing and livestock industries, and these odors cause problems that directly harm the human body, such as discomfort, vomiting, and headaches, or cause environmental pollution such as air pollution. I have it. In particular, such odors include acidic gases including hydrogen sulfide and mercatan, and alkaline gases including ammonia and amine gases, which are frequently generated in various high-pressure gas mixing devices, analyzers, and chemical plants.

따라서, 다각적인 방면에서 악취가스를 제거하기 위한 연구가 진행되고 있으며, 그에 따른 많은 악취 처리 기술이 공지되어 있다. 현재 사용되고 있는 악취가스 처리 기술로는 크게 물리적 처리방법, ㅎ화학적 처리방법 및 생물학적 처리방법으로 분류된다.Therefore, research is being conducted to remove odor gases from various aspects, and many odor treatment technologies are known accordingly. Currently used odor gas treatment technologies are largely classified into physical treatment methods, chemical treatment methods, and biological treatment methods.

물리적 처리방법으로는 활성탄 흡착탑이 알려져 있으며, 이러한 활성탄 흡착탑은 다공성의 활성탄을 내부에 충진하여 유입된 악취가스에 포함된 악취물질을 활성탄에 흡착함으로써 정화된 가스만을 흡착탑 외부로 배출하는 장치이다.As a physical treatment method, an activated carbon adsorption tower is known. This activated carbon adsorption tower is a device for discharging only the purified gas to the outside of the adsorption tower by adsorbing odorous substances contained in the inflowed odor gas to the activated carbon by filling porous activated carbon therein.

대한민국 등록특허 제10-1130323호에서는 가스를 정화하는 활성탄 흡착탑으로서, 활성탄 흡착탑의 외부에서 내부로 가스가 유입되는 유입구와, 유입구를 통해 유입된 가스가 유동하는 유입로와, 유입로를 중심으로 상부에 위치하는 상부 활성탄층과, 유입로를 중심으로 하부에 위치하는 하부 활성탄층과, 상부 활성탄층을 통과한 가스가 유동하는 상부 유동로와, 하부 활성탄층을 통과한 가스가 유동하는 하부 유동로와, 각 유동로들을 따라 유동한 가스가 외부로 배출되도록 형성된 배출구를 포함하며, 상부 활성탄층은 유입로 상부에 점착성 활성탄이 충진되고 점착성 활성탄의 상부에 비점착성 활성탄이 충진되며, 하부 활성탄층은 유입로 하부에 점착성 활성탄이 충진되고 점착성 활성탄의 하부에 비점착성 활성탄이 충진된 것을 특징으로 하는 활성탄 흡착탑을 제시하고 있다.Korean Patent Registration No. 10-1130323 discloses an activated carbon adsorption tower for purifying gas, an inlet through which gas flows from the outside to the inside of the activated carbon adsorption tower, an inlet through which the gas introduced through the inlet flows, and an upper part centered on the inlet. An upper activated carbon layer located at the center, a lower activated carbon layer located below the inlet passage, an upper flow path through which gas passed through the upper activated carbon layer flows, and a lower flow path through which gas passed through the lower activated carbon layer flows. And, an outlet formed to discharge gas flowing along each flow passage to the outside, wherein the upper activated carbon layer has adhesive activated carbon filled at the top of the inlet passage and non-adhesive activated carbon filled on top of the adhesive activated carbon, and the lower activated carbon layer has An activated carbon adsorption tower characterized in that the bottom of the inlet is filled with viscous activated carbon and the bottom of the inlet is filled with non-adhesive activated carbon.

그러나, 현재로서는 황화수소를 포함하는 산성가스와 암모니아를 포함하는 알칼리성가스를 처리하기에 처리성능의 저하 문제가 있다.However, at present, there is a problem of deterioration in treatment performance in treating acidic gas containing hydrogen sulfide and alkaline gas containing ammonia.

한편, 원두커피를 가공하고 남은 찌꺼기(커피박, coffee grounds)는 커피 제조 공장 및 일반 커피 전문점에서 유기질폐기물로서 처리되거나, 수거되어 일반 사료의 배합물로서 이용되고 있다. 최근에 이러한 커피박을 탈취제로서 이용하거나 유기질비료의 성분으로 이용하고자 하는 시도의 다양성을 표면상으로 갖고 있으나, 아직까지도 폭 넓고 구체적 연구에 따른 재활용의 연구는 다소 부족한 실정으로 판단된다.On the other hand, coffee grounds (coffee grounds) remaining after processing coffee beans are treated as organic waste at coffee manufacturing plants and general coffee shops, or are collected and used as a mixture of general feed. Recently, there have been various attempts to use these coffee wastes as a deodorant or as a component of organic fertilizer on the surface, but research on recycling according to a wide and specific study is still judged to be somewhat insufficient.

본 발명은 상기와 같은 문제점 중의 한가지로서 해결하기 위해 안출된 것으로서, 본 발명의 목적은 커피박 활성탄과 폐흡착제를 포함하는 흡착제로서 황화수소 등의 산성가스 및 암모니아 등의 알칼리성가스를 포함하는 악취 가스 정화용 흡착제를 제공하는 것이다.The present invention has been made to solve one of the above problems, and an object of the present invention is an adsorbent comprising coffee ground activated carbon and a waste adsorbent for purifying odorous gases including acidic gases such as hydrogen sulfide and alkaline gases such as ammonia. to provide an adsorbent.

본 발명의 과제는 이상에서 언급한 과제들로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.The object of the present invention is not limited to the tasks mentioned above, and other tasks not mentioned will be clearly understood by those skilled in the art from the following description.

상기 목적을 달성하기 위하여 본 발명은In order to achieve the above object, the present invention

커피박 활성탄을 포함하는 산성 및 알칼리성 악취 정화용 복합 흡착제를 제공한다.Provided is a composite adsorbent for purifying acidic and alkaline odors containing activated carbon from coffee grounds.

또한, 상기 복합 흡착제는 커피박 활성탄 38-42 중량부, 폐흡착제 3-7 중량부, 폐석고분말 7-11 중량부, 수산화철이 함유된 무기성오니 7-11 중량부, 아스코르브산 또는 구연산 2.5-4.5 중량부, 제올라이트 14-18 중량부, 벤토나이트 10-14 중량부 및 수산화칼륨 4.5-6.5 중량부를 포함하는 것을 특징으로 한다.In addition, the composite adsorbent is 38-42 parts by weight of coffee ground activated carbon, 3-7 parts by weight of waste adsorbent, 7-11 parts by weight of waste gypsum powder, 7-11 parts by weight of inorganic sludge containing iron hydroxide, ascorbic acid or citric acid 2.5- 4.5 parts by weight, 14-18 parts by weight of zeolite, 10-14 parts by weight of bentonite and 4.5-6.5 parts by weight of potassium hydroxide.

또한, 본 발명은In addition, the present invention

커피박을 식품첨가물용 인산 수용액으로 세척하여 불순물을 제거하는 단계; 불순물이 제거된 커피박을 아염소산나트륨 및 초산을 1:1의 중량비율로 혼합한 혼합용액에 침지하고 25-35℃의 온도에서 80-100분 동안 1차 전처리하는 단계; 1차 전처리된 커피박을 수산화칼륨 수용액에 침지하고 40-50℃의 온도에서 50-70분 동안 2차 전처리하는 단계; 2차 전처리된 커피박을 170-190℃의 온도에서 11-13시간 동안 1차 열처리하는 단계; 1차 열처리된 커피박을 410-430℃의 온도에서 2-4시간 동안 2차 열처리하는 단계; 및 2차 열처리된 커피박을 700-900℃의 온도에서 45-75분 동안 탄화하여 활성탄을 제조하는 단계;를 포함하는 커피박으로부터 활성탄을 제조하는 단계; 및Washing the coffee grounds with an aqueous phosphoric acid solution for food additives to remove impurities; immersing the coffee grounds from which impurities are removed in a mixed solution of sodium chlorite and acetic acid mixed at a weight ratio of 1:1 and pre-treating at a temperature of 25-35 ° C. for 80-100 minutes; immersing the first pre-treated coffee grounds in an aqueous solution of potassium hydroxide and performing a second pre-treatment at a temperature of 40-50 ° C. for 50-70 minutes; Primary heat treatment of the second pre-treated coffee waste at a temperature of 170-190 ° C. for 11-13 hours; Secondary heat treatment of the first heat-treated coffee waste at a temperature of 410-430 ° C. for 2-4 hours; Preparing activated carbon from coffee waste; and

커피박으로부터 제조된 활성탄 38-42 중량부, 폐흡착제 3-7 중량부, 폐석고분말 7-11 중량부, 수산화철이 함유된 무기성오니 7-11 중량부, 아스코르브산 또는 구연산 2.5-4.5 중량부, 제올라이트 14-18 중량부, 벤토나이트 10-14 중량부 및 수산화칼륨 4.5-6.5 중량부를 혼합하고 350-450℃의 온도에서 열처리하는 단계;를 포함하는 복합 흡착제의 제조방법을 제공한다.38-42 parts by weight of activated carbon prepared from coffee waste, 3-7 parts by weight of waste adsorbent, 7-11 parts by weight of waste gypsum powder, 7-11 parts by weight of inorganic sludge containing iron hydroxide, 2.5-4.5 parts by weight of ascorbic acid or citric acid , mixing 14-18 parts by weight of zeolite, 10-14 parts by weight of bentonite and 4.5-6.5 parts by weight of potassium hydroxide and heat-treating at a temperature of 350-450 ° C.

본 발명에 따른 복합 흡착제는 악취 가스에 포함된 황화수소 등의 산성가스 및 암모니아 등의 알칼리성가스를 동시에 제거 가능한 흡착제로, 우수한 제거 성능을 나타낸다. 또한, 산소와의 철 접촉 반응에 따른 발열반응이 없다.The composite adsorbent according to the present invention is an adsorbent capable of simultaneously removing acidic gases such as hydrogen sulfide and alkaline gases such as ammonia contained in malodorous gases, and exhibits excellent removal performance. In addition, there is no exothermic reaction according to the iron contact reaction with oxygen.

도 1은 본 발명에 따른 복합 흡착제의 제조방법을 순서도로 나타낸 것이다.1 is a flow chart showing a method for preparing a composite adsorbent according to the present invention.

이하에서는 첨부된 도면을 참조하여 다양한 실시예를 보다 상세하게 설명한다. 본 명세서에 기재된 실시예는 다양하게 변형될 수 있다. 특정한 실시예가 도면에서 묘사되고 상세한 설명에서 자세하게 설명될 수 있다. 그러나 첨부된 도면에 개시된 특정한 실시 예는 다양한 실시예를 쉽게 이해하도록 하기 위한 것일 뿐이다. 따라서 첨부된 도면에 개시된 특정 실시예에 의해 기술적 사상이 제한되는 것은 아니며, 발명의 사상 및 기술 범위에 포함되는 모든 균등물 또는 대체물을 포함하는 것으로 이해되어야 한다.Hereinafter, various embodiments will be described in more detail with reference to the accompanying drawings. The embodiments described in this specification may be modified in various ways. Certain embodiments may be depicted in the drawings and described in detail in the detailed description. However, specific embodiments disclosed in the accompanying drawings are only intended to facilitate understanding of various embodiments. Therefore, the technical idea is not limited by the specific embodiments disclosed in the accompanying drawings, and it should be understood to include all equivalents or substitutes included in the spirit and technical scope of the invention.

1차, 2차, 제1, 제2 등과 같이 서수를 포함하는 용어는 다양한 구성요소들을 설명하는데 사용될 수 있지만, 이러한 구성요소들은 상술한 용어에 의해 한정되지는 않는다. 상술한 용어는 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로만 사용된다.Terms including ordinal numbers such as primary, secondary, first, and second may be used to describe various elements, but these elements are not limited by the above-mentioned terms. The terminology described above is only used for the purpose of distinguishing one component from another.

본 명세서에서, '포함한다' 또는 '가지다' 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. 어떤 구성요소가 다른 구성요소에 '연결되어' 있다거나 '접속되어' 있다고 언급된 때에는, 그 다른 구성요소에 직접적으로 연결되어 있거나 또는 접속되어 있을 수도 있지만, 중간에 다른 구성요소가 존재할 수도 있다고 이해되어야 할 것이다. 반면에, 어떤 구성요소가 다른 구성요소에 '직접 연결되어' 있다거나 '직접 접속되어' 있다고 언급된 때에는, 중간에 다른 구성요소가 존재하지 않는 것으로 이해되어야 할 것이다.In this specification, terms such as 'comprise' or 'having' are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded. It is understood that when a component is referred to as being 'connected' or 'connected' to another component, it may be directly connected or connected to the other component, but other components may exist in the middle. It should be. On the other hand, when a component is referred to as being 'directly connected' or 'directly connected' to another component, it should be understood that no other component exists in the middle.

그 밖에도, 본 발명을 설명함에 있어서, 관련된 공지 기능 혹은 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우, 그에 대한 상세한 설명은 축약하거나 생략한다.In addition, in describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be abbreviated or omitted.

본 발명은 커피박 활성탄을 포함하는 산성 및 알칼리성 악취 정화용 복합 흡착제를 제공한다.The present invention provides a composite adsorbent for purifying acidic and alkaline odors containing activated carbon from coffee grounds.

이하, 본 발명에 따른 복합 흡착제에 대하여 상세히 설명한다.Hereinafter, the composite adsorbent according to the present invention will be described in detail.

상기 흡착제는 커피박 활성탄 38-42 중량부, 폐흡착제 3-7 중량부, 폐석고분말 7-11 중량부, 수산화철이 함유된 무기성오니 7-11 중량부, 아스코르브산 또는 구연산 2.5-4.5 중량부, 제올라이트 14-18 중량부, 벤토나이트 10-14 중량부 및 수산화칼륨 4.5-6.5 중량부를 포함하는 것이 바람직하고, 커피박 활성탄 39-41 중량부, 폐흡착제 4-6 중량부, 폐석고분말 8-10 중량부, 수산화철이 함유된 무기성오니 8-10 중량부, 아스코르브산 또는 구연산 3-4 중량부, 제올라이트 15-17 중량부, 벤토나이트 11-13 중량부 및 수산화칼륨 5-6 중량부를 포함하는 것이 더욱 바람직하고, 커피박 활성탄 40 중량부, 폐흡착제 5 중량부, 폐석고분말 9 중량부, 무기성오니 9 중량부, 아스코르브산 3.5, 제올라이트 16 중량부, 벤토나이트 12 중량부 및 수산화칼륨 5.5 중량부를 포함하는 것이 가장 바람직하다.The adsorbent includes 38-42 parts by weight of coffee ground activated carbon, 3-7 parts by weight of waste adsorbent, 7-11 parts by weight of waste gypsum powder, 7-11 parts by weight of inorganic sludge containing iron hydroxide, and 2.5-4.5 parts by weight of ascorbic acid or citric acid. , preferably containing 14-18 parts by weight of zeolite, 10-14 parts by weight of bentonite and 4.5-6.5 parts by weight of potassium hydroxide, 39-41 parts by weight of coffee ground activated carbon, 4-6 parts by weight of waste adsorbent, 8-10 parts by weight of waste gypsum powder 8-10 parts by weight of inorganic sludge containing iron hydroxide, 3-4 parts by weight of ascorbic acid or citric acid, 15-17 parts by weight of zeolite, 11-13 parts by weight of bentonite and 5-6 parts by weight of potassium hydroxide More preferably, it contains 40 parts by weight of coffee ground activated carbon, 5 parts by weight of waste adsorbent, 9 parts by weight of waste gypsum powder, 9 parts by weight of inorganic sludge, 3.5 parts by weight of ascorbic acid, 16 parts by weight of zeolite, 12 parts by weight of bentonite and 5.5 parts by weight of potassium hydroxide. It is most preferable to

상기 커피박 활성탄은 커피박으로부터 제조된 활성탄으로, 커피박을 재활용할 수 있다. 구체적으로, 상기 커피박 활성탄은, 커피박을 인산 수용액으로 세척하여 불순물을 제거하는 단계; 불순물이 제거된 커피박을 아염소산나트륨 및 초산을 1:1의 중량비율로 혼합한 혼합용액에 침지하고 25-35℃의 온도에서 80-100분 동안 1차 전처리하는 단계; 1차 전처리된 커피박을 수산화칼륨 수용액에 침지하고 40-50℃의 온도에서 50-70분 동안 2차 전처리하는 단계; 2차 전처리된 커피박을 170-190℃의 온도에서 11-13시간 동안 1차 열처리하는 단계; 1차 열처리된 커피박을 410-430℃의 온도에서 2-4시간 동안 2차 열처리하는 단계; 및 2차 열처리된 커피박을 700-900℃의 온도에서 45-75분 동안 탄화하여 활성탄을 제조하는 단계;를 수행하여 제조되는 것을 사용한다.The coffee ground activated carbon is activated carbon prepared from coffee grounds, and the coffee grounds can be recycled. Specifically, the coffee ground activated carbon is prepared by washing the coffee grounds with an aqueous phosphoric acid solution to remove impurities; immersing the coffee grounds from which impurities are removed in a mixed solution of sodium chlorite and acetic acid mixed at a weight ratio of 1:1 and pre-treating at a temperature of 25-35 ° C. for 80-100 minutes; immersing the first pre-treated coffee grounds in an aqueous solution of potassium hydroxide and performing a second pre-treatment at a temperature of 40-50 ° C. for 50-70 minutes; Primary heat treatment of the second pre-treated coffee waste at a temperature of 170-190 ° C. for 11-13 hours; Secondary heat treatment of the first heat-treated coffee waste at a temperature of 410-430 ° C. for 2-4 hours; and preparing activated carbon by carbonizing the secondary heat-treated coffee waste at a temperature of 700-900 ° C. for 45-75 minutes.

상기 폐흡착제는 탈황제로 사용된 폐흡착제로, 황화수소 등을 흡착시킨 흡착제에서 흡착된 황화수소를 제거하고 황화수소가 제거된 흡착제를 분쇄한 것을 사용하는 것이 바람직하다. 황화수소 제거는 폐흡착제를 400-500℃의 온도로 가열하여 수행될 수 있다. 상기 폐흡착제는 철 성분을 포함하고, 이는 황화수소 등의 산성가스를 제거하는 데 용이하다.The waste adsorbent is a waste adsorbent used as a desulfurization agent, and it is preferable to use an adsorbent obtained by removing hydrogen sulfide adsorbed from an adsorbent adsorbing hydrogen sulfide or the like and pulverizing the adsorbent from which the hydrogen sulfide is removed. Removal of hydrogen sulfide may be performed by heating the spent adsorbent to a temperature of 400-500 °C. The waste adsorbent contains an iron component, and it is easy to remove acid gases such as hydrogen sulfide.

상기 폐석고분말은 황산철이 함유된 것이 바람직하고, 복합 흡착제의 바인더로서 역할을 하며 더불어 철 성분을 포함하여 황화수소, 메르카탄류 등을 포함하는 산성가스를 제거하는 데 용이하다.The waste gypsum powder preferably contains iron sulfate, serves as a binder for the composite adsorbent, and is easy to remove acid gases including hydrogen sulfide and mercatanes, including iron components.

상기 무기성오니는 제철 제강회사에서 나오는 폐슬러지인 것이 바람직하고, 복합 흡착제의 바인더로서 역할을 하며 더불어 철 성분을 다량 포함하여 황화수소, 메르카탄류 등을 포함하는 산성가스를 제거하는 데 용이하다.The inorganic sludge is preferably waste sludge from iron and steel manufacturing companies, serves as a binder for the composite adsorbent, and is easy to remove acid gases including hydrogen sulfide and mercatanes as it contains a large amount of iron.

상기 아스코르브산 또는 구연산을 복합 흡착제에 적용하여 폐석고분말 또는 무기성오니에 포함된 황산철, 수산화철 성분을 킬레이트화하며 이를 통해 황화수소, 메르카탄류 등을 포함하는 산성가스를 제거하는 데 용이하도록 구성한다.The ascorbic acid or citric acid is applied to the composite adsorbent to chelate the iron sulfate and iron hydroxide components contained in the waste gypsum powder or inorganic sludge, thereby facilitating the removal of acid gases including hydrogen sulfide and mercatanes. .

상기 제올라이트는 양이온 치환능력을 가지고 있어 암모니아, 아민류가스 등을 포함하는 알칼리성가스를 제거하는 데 용이하다.Since the zeolite has a cation exchange ability, it is easy to remove alkaline gases including ammonia and amine gases.

상기 벤토나이트는 바인더 역할과 함께 양이온 치환능력을 가지고 있어 암모니아, 아민류가스 등을 포함하는 알칼리성가스를 제거하는 데 용이하다.The bentonite serves as a binder and has a cation substitution ability, so it is easy to remove alkaline gases including ammonia and amine gases.

상기 수산화칼륨은 산성가스 또는 알칼리성가스의 흡착 성능을 더욱 올려준다.The potassium hydroxide further increases adsorption performance of acidic gas or alkaline gas.

본 발명에 따른 복합 흡착제는 악취 가스에 포함된 황화수소 등의 산성가스 및 암모니아 등의 알칼리성가스를 동시에 제거 가능한 흡착제로, 우수한 제거 성능과 산소와의 철 접촉 반응에 따른 발열반응이 없다.The composite adsorbent according to the present invention is an adsorbent capable of simultaneously removing acidic gases such as hydrogen sulfide and alkaline gases such as ammonia contained in malodorous gases, and has excellent removal performance and no exothermic reaction due to iron contact reaction with oxygen.

또한, 본 발명은In addition, the present invention

커피박을 인산 수용액으로 세척하여 불순물을 제거하는 단계; 불순물이 제거된 커피박을 아염소산나트륨 및 초산을 1:1의 중량비율로 혼합한 혼합용액에 침지하고 25-35℃의 온도에서 80-100분 동안 1차 전처리하는 단계; 1차 전처리된 커피박을 수산화칼륨 수용액에 침지하고 40-50℃의 온도에서 50-70분 동안 2차 전처리하는 단계; 2차 전처리된 커피박을 170-190℃의 온도에서 11-13시간 동안 1차 열처리하는 단계; 1차 열처리된 커피박을 410-430℃의 온도에서 2-4시간 동안 2차 열처리하는 단계; 및 2차 열처리된 커피박을 700-900℃의 온도에서 45-75분 동안 탄화하여 활성탄을 제조하는 단계;를 포함하는 커피박으로부터 활성탄을 제조하는 단계; 및Washing the coffee grounds with an aqueous phosphoric acid solution to remove impurities; immersing the coffee grounds from which impurities are removed in a mixed solution of sodium chlorite and acetic acid mixed at a weight ratio of 1:1 and pre-treating at a temperature of 25-35 ° C. for 80-100 minutes; immersing the first pre-treated coffee grounds in an aqueous solution of potassium hydroxide and performing a second pre-treatment at a temperature of 40-50 ° C. for 50-70 minutes; Primary heat treatment of the second pre-treated coffee waste at a temperature of 170-190 ° C. for 11-13 hours; Secondary heat treatment of the first heat-treated coffee waste at a temperature of 410-430 ° C. for 2-4 hours; Preparing activated carbon from coffee waste; and

커피박으로부터 제조된 활성탄 38-42 중량부, 폐흡착제 3-7 중량부, 폐석고분말 7-11 중량부, 수산화철이 함유된 무기성오니 7-11 중량부, 아스코르브산 또는 구연산 2.5-4.5 중량부, 제올라이트 14-18 중량부, 벤토나이트 10-14 중량부 및 수산화칼륨 4.5-6.5 중량부를 혼합하고 350-450℃의 온도에서 열처리하는 단계;를 포함하는 복합 흡착제의 제조방법을 제공한다.38-42 parts by weight of activated carbon prepared from coffee waste, 3-7 parts by weight of waste adsorbent, 7-11 parts by weight of waste gypsum powder, 7-11 parts by weight of inorganic sludge containing iron hydroxide, 2.5-4.5 parts by weight of ascorbic acid or citric acid , mixing 14-18 parts by weight of zeolite, 10-14 parts by weight of bentonite and 4.5-6.5 parts by weight of potassium hydroxide and heat-treating at a temperature of 350-450 ° C.

이때, 도 1에 본 발명에 따른 복합 흡착제의 제조방법을 순서도로 나타내었으며, 이하, 본 발명에 따른 복합 흡착제의 제조방법을 각 단계별로 상세히 설명한다.At this time, the manufacturing method of the composite adsorbent according to the present invention is shown in a flow chart in FIG. 1, and hereinafter, the manufacturing method of the composite adsorbent according to the present invention will be described in detail for each step.

먼저, 본 발명에 따른 복합 흡착제의 제조방법은 커피박으로부터 활성탄을 제조하는 단계를 포함한다.First, the manufacturing method of the composite adsorbent according to the present invention includes preparing activated carbon from coffee grounds.

상기 커피박으로부터 활성탄을 제조하는 단계는,The step of preparing activated carbon from the coffee waste,

커피박을 인산 수용액으로 세척하여 불순물을 제거하는 단계; Washing the coffee grounds with an aqueous phosphoric acid solution to remove impurities;

불순물이 제거된 커피박을 아염소산나트륨 및 초산을 1:1의 중량비율로 혼합한 혼합용액에 침지하고 25-35℃의 온도에서 80-100분 동안 1차 전처리하는 단계;immersing the coffee grounds from which impurities are removed in a mixed solution of sodium chlorite and acetic acid mixed at a weight ratio of 1:1 and pre-treating at a temperature of 25-35 ° C. for 80-100 minutes;

1차 전처리된 커피박을 수산화칼륨 수용액에 침지하고 40-50℃의 온도에서 50-70분 동안 2차 전처리하는 단계;immersing the first pre-treated coffee grounds in an aqueous solution of potassium hydroxide and performing a second pre-treatment at a temperature of 40-50 ° C. for 50-70 minutes;

2차 전처리된 커피박을 170-190℃의 온도에서 11-13시간 동안 1차 열처리하는 단계;Primary heat treatment of the second pre-treated coffee waste at a temperature of 170-190 ° C. for 11-13 hours;

1차 열처리된 커피박을 410-430℃의 온도에서 2-4시간 동안 2차 열처리하는 단계; 및Secondary heat treatment of the first heat-treated coffee waste at a temperature of 410-430 ° C. for 2-4 hours; and

2차 열처리된 커피박을 700-900℃의 온도에서 45-75분 동안 탄화하여 활성탄을 제조하는 단계;를 포함한다.Carbonizing the secondary heat-treated coffee waste at a temperature of 700-900 ° C. for 45-75 minutes to prepare activated carbon; includes.

먼저, 커피박을 인산 수용액으로 세척하여 불순물을 제거한다.First, the coffee grounds are washed with an aqueous phosphoric acid solution to remove impurities.

상기에서는 커피박을 인산 수용액으로 세척한다. 이를 통해 커피박의 불순물을 효과적으로 제거할 수 있다. 여기서 인산 수용액을 적정 사용함으로써 지나친 산도로 인해 커피박이 손상되거나 녹는 문제를 해결하고 효과적으로 불순물을 제거할 수 있다.In the above, the coffee waste is washed with an aqueous phosphoric acid solution. Through this, impurities in the coffee waste can be effectively removed. Here, by appropriately using an aqueous phosphoric acid solution, it is possible to solve the problem of damage or melting of coffee grounds due to excessive acidity and to effectively remove impurities.

불순물을 제거하고 난 후 커피박을 분쇄하여 분말로 형성하여 사용하는 것이 바람직하다. 분말화하여 이후 단계를 진행함으로써 더욱 효과적으로 전처리, 열처리 및 탄화를 수행할 수 있다.After removing impurities, it is preferable to grind the coffee grounds and form them into powder before use. By powdering and proceeding with subsequent steps, pretreatment, heat treatment and carbonization can be performed more effectively.

다음, 불순물이 제거된 커피박을 아염소산나트륨 및 초산을 1:1의 중량비율로 혼합한 혼합용액에 침지하고 25-35℃의 온도에서 80-100분 동안 1차 전처리한다.Next, the coffee waste from which impurities are removed is immersed in a mixed solution of sodium chlorite and acetic acid mixed in a weight ratio of 1: 1, and subjected to a first pretreatment at a temperature of 25-35 ° C for 80-100 minutes.

상기에서는 불순물이 제거된 커피박을 아염소산나트륨 및 초산의 혼합용액에 침지하여 1차 전처리한다.In the above, the coffee waste from which impurities are removed is immersed in a mixed solution of sodium chlorite and acetic acid to perform a first pretreatment.

이러한 1차 전처리는 커피박을 활성탄으로 형성함에 있어서 비표면적을 더욱 높이고 효과적으로 활성화시키기 위해 수행되는 과정이다.This first pretreatment is a process performed to further increase the specific surface area and effectively activate it in forming the coffee waste into activated carbon.

다음, 1차 전처리된 커피박을 수산화칼륨 수용액에 침지하고 40-50℃의 온도에서 50-70분 동안 2차 전처리한다.Next, the first pre-treated coffee grounds are immersed in an aqueous solution of potassium hydroxide, and the second pre-treatment is performed at a temperature of 40-50 ° C. for 50-70 minutes.

상기에서는 1차 전처리된 커피박을 수산화칼륨 수용액에 침지하여 2차 전처리를 수행한다.In the above, a second pretreatment is performed by immersing the first pretreated coffee grounds in an aqueous solution of potassium hydroxide.

이러한 2차 전처리는 커피박을 활성탄으로 형성함에 있어서 미세 기공을 형성하여 비표면적을 향상시킬 수 있으며, 커피박에 포함된 수분을 제거하여 효과적으로 활성화시키기 위해 수행되는 과정이다.This secondary pretreatment can improve the specific surface area by forming micropores in forming the coffee waste with activated carbon, and is a process performed to effectively activate the coffee waste by removing moisture contained in the coffee waste.

다음, 2차 전처리된 커피박을 170-190℃의 온도에서 11-13시간 동안 1차 열처리한다.Next, the second pre-treated coffee waste is subjected to a first heat treatment at a temperature of 170-190 ° C for 11-13 hours.

상기에서는 1차 열처리를 수행한다.In the above, the first heat treatment is performed.

상기 1차 전처리 및 2차 전처리를 수행하고난 후, 전처리된 커피박을 170-190℃의 온도에서 11-13시간 동안 1차 열처리하여 커피박에 포함된 잔여물을 제거하고 활성화 준비를 한다. 상기 1차 열처리를 170℃ 미만의 온도에서 수행하는 경우 잔여물 제거가 충분히 수행되지 않는 문제가 있고, 190℃ 초과의 온도에서 수행하는 경우 후단의 탄화 공정에서 수득률이 낮아지는 문제가 있다.After performing the first pre-treatment and the second pre-treatment, the pre-treated coffee waste is subjected to a first heat treatment at a temperature of 170-190 ° C. for 11-13 hours to remove residues contained in the coffee waste and prepare for activation. When the first heat treatment is performed at a temperature of less than 170 ° C., there is a problem in that the residue is not sufficiently removed, and when the temperature is greater than 190 ° C., the yield in the subsequent carbonization process is lowered.

다음, 1차 열처리된 커피박을 410-430℃의 온도에서 2-4시간 동안 2차 열처리한다.Next, the coffee grounds subjected to the first heat treatment are subjected to a second heat treatment at a temperature of 410-430 ° C for 2-4 hours.

상기에서는 2차 열처리를 수행한다.In the above, a secondary heat treatment is performed.

상기 1차 열처리를 수행하고난 후, 1차 열처리된 커피박을 410-430℃의 온도에서 2-4시간 동안 2차 열처리하여 탄소 성분 외에는 열분해로 제거하면서 일부 기공을 형성하게 된다. 상기 2차 열처리를 410℃ 미만의 온도에서 수행하는 경우 열분해가 수행되지 않는 문제가 있으며, 430℃ 초과의 온도에서 수행하는 경우 후단의 탄화 공정에서 수득률이 낮아지는 문제가 있다.After performing the first heat treatment, the first heat treatment coffee waste is subjected to a second heat treatment at a temperature of 410-430 ° C. for 2-4 hours to form some pores while removing carbon components by pyrolysis. When the secondary heat treatment is performed at a temperature of less than 410 ° C., there is a problem in that thermal decomposition is not performed, and when performed at a temperature of more than 430 ° C., there is a problem in that the yield in the subsequent carbonization process is lowered.

다음, 2차 열처리된 커피박을 700-900℃의 온도에서 45-75분 동안 탄화하여 활성탄을 제조한다.Next, activated carbon is prepared by carbonizing the secondary heat-treated coffee waste at a temperature of 700-900 ° C. for 45-75 minutes.

상기에서는 탄화공정을 수행하여 활성탄을 형성한다.In the above, a carbonization process is performed to form activated carbon.

상기 2차 열처리를 수행하고난 후, 2차 열처리된 커피박을 700-900℃의 온도에서 45-75분 동안 탄화하여 활성탄을 제조하며, 바람직하게는 상기 2차 열처리된 커피박 75-85 중량부 및 변성 전분 15-25 중량부를 혼합한 혼합물을 이용하여 900℃의 온도에서 60분 동안 탄화하여 활성탄을 제조한다.After performing the second heat treatment, the second heat treatment coffee waste is carbonized at a temperature of 700-900 ° C. for 45-75 minutes to prepare activated carbon, preferably the second heat treatment coffee waste 75-85 weight Activated carbon is prepared by carbonizing at a temperature of 900° C. for 60 minutes using a mixture of 15 to 25 parts by weight of starch and modified starch.

상기 커피박만을 이용하여 탄화하여 활성탄을 제조하는 경우 높은 비표면적을 확보할 수는 있으나 물성이 부족하여 흡착제로서 적용하는 경우 흡착성능이 저하되는 문제가 있다. 이에, 상기 커피박에 변성 전분을 혼합한 혼합물을 이용하여 900℃의 고온에서 탄화하여 활성탄을 제조하며, 이 경우 더욱 높은 비표면적을 나타냄과 동시에 안전한 물성을 확보할 수 있어 흡착제로서 적용하는 경우 흡착성능이 매우 우수하다.When activated carbon is produced by carbonization using only the coffee waste, a high specific surface area can be secured, but when applied as an adsorbent due to insufficient physical properties, there is a problem in that adsorption performance is lowered. Therefore, activated carbon is prepared by carbonizing at a high temperature of 900 ° C. using a mixture of modified starch in the coffee waste. In this case, it is possible to obtain a higher specific surface area and secure physical properties, so that when applied as an adsorbent, adsorption Performance is very good.

상기 변성 전분은 산화 에스테르화 전분인 것이 바람직하고, 카르복실기 함량이 0.5-0.8%이고, 아세틸기 함량이 0.3-0.7%인 산화 에스테르화 전분인 것이 더욱 바람직하다. 상기 산화 에스테르화 전분은 전분 슬러리에 산화제를 첨가하고 산화 반응시켜 카르복실기 함량이 0.5-0.8%인 산화 전분의 슬러리를 수득하고, 산화 전분의 슬러리에 에스테르화제를 첨가하고 에스테르화 반응시켜 아세틸기 함량이 0.3-0.7%인 산화 에스테르화 전분의 슬러리를 수득하고, 산화 에스테르화 전분의 슬러리를 여과, 세척 및 건조시켜 산화 에스테르화 전분을 수득하여 제조되는 것을 사용한다. 상기 산화제는 아염소산나트륨, 차아염소산나트륨, 염소화이소시아누르산, 과산화수소, 과붕산나트륨 및 과망간산칼륨 등일 수 있고, 상기 에스테르화제는 무수초산, 무수말레산 및 초산비닐 단량체 등일 수 있다.The modified starch is preferably oxidized esterified starch, more preferably oxidized esterified starch having a carboxyl group content of 0.5-0.8% and an acetyl group content of 0.3-0.7%. The oxidized esterified starch is obtained by adding an oxidizing agent to the starch slurry and performing an oxidation reaction to obtain an oxidized starch slurry having a carboxyl group content of 0.5-0.8%, adding an esterifying agent to the oxidized starch slurry and performing an esterification reaction to obtain an acetyl group content A slurry of 0.3-0.7% oxidized esterified starch is obtained, and the slurry of oxidized esterified starch is filtered, washed and dried to obtain oxidized esterified starch. The oxidizing agent may be sodium chlorite, sodium hypochlorite, chlorinated isocyanuric acid, hydrogen peroxide, sodium perborate and potassium permanganate, and the like, and the esterifying agent may be acetic anhydride, maleic anhydride and vinyl acetate monomer.

또한, 제조된 활성탄을 물에 침지 후 교반하여 세척하는 단계를 포함할 수 있다. 상기에서는 커피박으로부터 제조된 활성탄을 물에 침지 후 교반하여 칼륨을 제거할 수 있다. 커피박으로부터 제조된 활성탄은 칼륨 등의 성분을 함유하고 있어 이를 제거하여 더욱 흡착제로서의 성능을 높일 수 있다. 다만, 악취정화용으로 사용할 때에는 상기의 세척 단계를 제외할 수 있다.In addition, a step of washing the prepared activated carbon by immersing it in water and stirring it may be included. In the above, potassium may be removed by immersing activated carbon prepared from coffee grounds in water and then stirring. Activated carbon prepared from coffee grounds contains components such as potassium, which can be removed to further improve performance as an adsorbent. However, when used for odor purification, the above washing step may be excluded.

또한, 세척된 활성탄을 건조하는 단계를 포함할 수 있다. 최종 건조과정을 통해 활성탄을 제조한다.In addition, a step of drying the washed activated carbon may be included. Activated carbon is prepared through a final drying process.

다음으로, 본 발명에 따른 복합 흡착제의 제조방법은 커피박으로부터 제조된 활성탄 38-42 중량부, 폐흡착제 3-7 중량부, 폐석고분말 7-11 중량부, 수산화철이 함유된 무기성오니 7-11 중량부, 아스코르브산 또는 구연산 2.5-4.5 중량부, 제올라이트 14-18 중량부, 벤토나이트 10-14 중량부 및 수산화칼륨 4.5-6.5 중량부를 혼합하고 350-450℃의 온도에서 열처리하는 단계를 포함한다.Next, the method for preparing the composite adsorbent according to the present invention includes 38-42 parts by weight of activated carbon prepared from coffee grounds, 3-7 parts by weight of waste adsorbent, 7-11 parts by weight of waste gypsum powder, and 7-11 parts by weight of inorganic sludge containing iron hydroxide. 11 parts by weight, 2.5-4.5 parts by weight of ascorbic acid or citric acid, 14-18 parts by weight of zeolite, 10-14 parts by weight of bentonite and 4.5-6.5 parts by weight of potassium hydroxide are mixed and heat-treated at a temperature of 350-450 ° C. .

상기 단계에서는 커피박 활성탄을 이용하여 폐흡착제, 폐석고분말, 무기성오니, 아스코르브산 또는 구연산, 제올라이트, 벤토나이트 및 수산화칼륨을 일정 함량 혼합하고 열처리하여 복합 흡착제를 제조한다.In the above step, a composite adsorbent is prepared by mixing a waste adsorbent, waste gypsum powder, inorganic sludge, ascorbic acid or citric acid, zeolite, bentonite, and potassium hydroxide in a predetermined amount using coffee ground activated carbon and heat-treating.

상기 폐흡착제는 탈황제로 사용된 폐흡착제인 것이 바람직하고, 황화수소를 포함하는 가스의 황화수소 제거에 사용된 흡착제에서 흡착된 황화수소를 제거하고 황화수소가 제거된 흡착제를 분쇄한 것을 사용하는 것이 바람직하다. 상기 폐흡착제는 황화수소 제거에 사용된 폐흡착제를 400-500℃의 온도로 가열하여 황화수소를 제거하고 이를 분쇄하여 분말 형태로 사용할 수 있다.The waste adsorbent is preferably a waste adsorbent used as a desulfurization agent, and it is preferable to use an adsorbent obtained by removing hydrogen sulfide adsorbed from an adsorbent used to remove hydrogen sulfide from a gas containing hydrogen sulfide and pulverizing the adsorbent from which the hydrogen sulfide is removed. The waste adsorbent used to remove hydrogen sulfide may be heated to a temperature of 400-500° C. to remove hydrogen sulfide, and then pulverized to be used in powder form.

상기 폐석고분말은 황산철이 함유된 것이 바람직하다.Preferably, the waste gypsum powder contains iron sulfate.

상기 무기성오니는 제철 제강회사에서 나오는 수산화철이 함유된 폐슬러지인 것이 바람직하다.The inorganic sludge is preferably waste sludge containing iron hydroxide from an iron or steel manufacturing company.

<제조예 1> 변성 전분 제조<Preparation Example 1> Preparation of modified starch

감자 전분 100 중량부 대비 물을 250 중량부 혼합하여 반응기에 넣어 전분 슬러리를 제조하였다. 전분 슬러리의 온도를 40℃로 조절하고, 반응기에 4% 수산화나트륨 수용액을 첨가하여 전분 슬러리의 pH를 8.0으로 조절하였다. 이후, 차아염소산나트륨 용액(활성염소 함량 : 14.5%) 50 중량부와 수산화나트륨 용액(33% 순도) 8 중량부 혼합한 혼합 용액을 반응기에 투입하고, 4% 수산화나트륨 수용액을 이용하여 pH를 9.5 이상으로 설정하고 120분 동안 반응시켜 전분을 산화 반응시켰다. 이후, 반응기에 메타중아황산나트륨을 미량 투입하여 산화반응을 완료시킨 후, 전분 슬러리의 온도를 32℃로 조절하고 여기에 15% 염산 수용액을 첨가하여 전분 슬러리의 pH를 8.2로 조절하였다. 이후, 무수초산(96% 순도) 5 중량부를 투입하며 5% 수산화나트륨 수용액으로 pH를 8.2로 유지시키며 전분을 에스테르화 반응시켰다. 에스테르화 반응 완료 후, 반응기에 15% 염산 수용액을 첨가하여 반응 생성물의 pH를 6.0으로 조절하고 여과한 다음 얻어진 고형물을 물로 세척하고 건조하여 산화 에스테르화 전분인 변성 전분을 제조하였다.A starch slurry was prepared by mixing 250 parts by weight of water with 100 parts by weight of potato starch and putting it into a reactor. The temperature of the starch slurry was adjusted to 40° C., and the pH of the starch slurry was adjusted to 8.0 by adding 4% sodium hydroxide aqueous solution to the reactor. Thereafter, a mixed solution obtained by mixing 50 parts by weight of sodium hypochlorite solution (active chlorine content: 14.5%) and 8 parts by weight of sodium hydroxide solution (33% purity) was introduced into the reactor, and the pH was adjusted to 9.5 using 4% sodium hydroxide aqueous solution. It was set above and reacted for 120 minutes to oxidize starch. Thereafter, after the oxidation reaction was completed by adding a small amount of sodium metabisulfite to the reactor, the temperature of the starch slurry was adjusted to 32° C., and a 15% aqueous hydrochloric acid solution was added thereto to adjust the pH of the starch slurry to 8.2. Thereafter, 5 parts by weight of acetic anhydride (96% purity) was added and the starch was esterified while maintaining the pH at 8.2 with a 5% sodium hydroxide aqueous solution. After completion of the esterification reaction, a 15% aqueous hydrochloric acid solution was added to the reactor to adjust the pH of the reaction product to 6.0, followed by filtration, and the obtained solid was washed with water and dried to prepare modified starch, which is oxidized esterified starch.

상기 변성 전분의 카르복실기 함량은 0.63%이고, 아세틸기 함량은 0.5%인 것을 확인하였다.It was confirmed that the modified starch had a carboxyl group content of 0.63% and an acetyl group content of 0.5%.

<제조예 2> 활성탄의 제조<Preparation Example 2> Preparation of activated carbon

커피박을 10 wt% 농도의 인산 수용액으로 세척하여 불순물을 제거하였다.The coffee grounds were washed with a 10 wt% aqueous phosphoric acid solution to remove impurities.

불순물이 제거된 커피박을 분쇄하여 커피박 분말을 형성하고, 커피박 분말을 아염소산나트륨 및 초산이 1:1의 중량비율로 혼합된 혼합용액에 침지시킨 후, 30℃의 온도를 유지하며 90분 동안 1차 전처리하였다.The coffee grounds from which impurities are removed are pulverized to form coffee grounds powder, and the coffee grounds powder is immersed in a mixed solution in which sodium chlorite and acetic acid are mixed in a weight ratio of 1:1, and then maintained at 30 ° C. 1st pre-treatment for 10 minutes.

1차 전처리 후, 커피박을 5 wt% 농도의 수산화칼륨 수용액에 침지시킨 후, 45℃의 온도를 유지하며 60분 동안 2차 전처리하였다.After the first pretreatment, the coffee grounds were immersed in an aqueous solution of potassium hydroxide having a concentration of 5 wt%, and then the second pretreatment was performed for 60 minutes while maintaining a temperature of 45 ° C.

2차 전처리 후, 커피박을 180℃의 온도에서 12시간 동안 1차 열처리하였다.After the second pretreatment, the coffee waste was subjected to a first heat treatment at a temperature of 180 ° C. for 12 hours.

1차 열처리 후, 커피박을 420℃의 온도에서 3시간 동안 2차 열처리하였다.After the first heat treatment, the coffee waste was subjected to a second heat treatment at a temperature of 420 ° C. for 3 hours.

2차 열처리 후, 커피박 80 중량부 및 상기 제조예 1에서 제조된 변성 전분 20 중량부를 혼합하고, 이를 700℃의 온도에서 60분 동안 탄화하여 활성탄을 형성하였다.After the secondary heat treatment, 80 parts by weight of coffee grounds and 20 parts by weight of the modified starch prepared in Preparation Example 1 were mixed, and carbonized at a temperature of 700 ° C. for 60 minutes to form activated carbon.

상기 활성탄을 물에 침지시켜 교반하여 세척한 후, 건조하여 활성탄을 제조하였다.The activated carbon was immersed in water, stirred, washed, and then dried to prepare activated carbon.

<제조예 3> 폐흡착제 제조<Preparation Example 3> Preparation of lung adsorbent

황화수소 제거에 사용된 폐흡착제를 수거하여 450℃의 온도에서 3시간 동안 열처리하여 황화수소를 제거한 후, 황화수소가 제거된 폐흡착제를 분쇄하여 폐흡착제 분말을 준비하였다.The waste adsorbent used to remove hydrogen sulfide was collected and heat-treated at a temperature of 450 ° C. for 3 hours to remove hydrogen sulfide, and then the waste adsorbent from which hydrogen sulfide was removed was pulverized to prepare a waste adsorbent powder.

<실시예 1> 복합 흡착제의 제조-1<Example 1> Preparation of composite adsorbent-1

상기 제조예 2에서 커피박으로부터 제조된 활성탄 40 중량부, 상기 제조예 3에서 준비된 폐흡착제 분말 5 중량부, 황산철이 함유된 폐석고분말 9 중량부, 제철제강회사에서 나오는 폐슬러지인 수산화철이 함유된 무기성오니 9 중량부, 아스코르브산 3.5 중량부, 제올라이트 분말 16 중량부, 벤토나이트 분말 12 중량부 및 수산화칼륨 5.5 중량부를 혼합하고 400℃의 온도로 열처리한 후, 압출성형하여 복합 흡착제를 제조하였다.40 parts by weight of activated carbon prepared from coffee grounds in Preparation Example 2, 5 parts by weight of waste adsorbent powder prepared in Preparation Example 3, 9 parts by weight of waste gypsum powder containing iron sulfate, waste sludge from steel mills containing iron hydroxide 9 parts by weight of inorganic sludge, 3.5 parts by weight of ascorbic acid, 16 parts by weight of zeolite powder, 12 parts by weight of bentonite powder, and 5.5 parts by weight of potassium hydroxide were mixed, heat-treated at 400° C., and then extruded to prepare a composite adsorbent.

<실시예 2> 복합 흡착제의 제조-2<Example 2> Preparation of composite adsorbent-2

상기 제조예 2에서 커피박으로부터 제조된 활성탄 45 중량부, 황산철이 함유된 폐석고분말 9 중량부, 제철제강회사에서 나오는 폐슬러지인 수산화철이 함유된 무기성오니 9 중량부, 아스코르브산 3.5 중량부, 제올라이트 분말 16 중량부, 벤토나이트 분말 12 중량부 및 수산화칼륨 5.5 중량부를 혼합하고 400℃의 온도로 열처리한 후, 압출성형하여 복합 흡착제를 제조하였다.45 parts by weight of activated carbon prepared from coffee waste in Preparation Example 2, 9 parts by weight of waste gypsum powder containing iron sulfate, 9 parts by weight of inorganic sludge containing iron hydroxide, which is waste sludge from steelmaking companies, 3.5 parts by weight of ascorbic acid, 16 parts by weight of zeolite powder, 12 parts by weight of bentonite powder, and 5.5 parts by weight of potassium hydroxide were mixed, heat-treated at a temperature of 400° C., and then extruded to prepare a composite adsorbent.

<실험예 1> 복합 흡착제의 악취 제거 성능 분석<Experimental Example 1> Analysis of odor removal performance of composite adsorbent

상기 실시예 1 및 실시예 2에서 제조된 복합 흡착제의 악취 제거 성능을 확인하기 위하여 황화수소 흡착량 및 암모니아 흡착량을 분석하였다.In order to confirm the odor removal performance of the composite adsorbents prepared in Examples 1 and 2, the amount of adsorption of hydrogen sulfide and the amount of adsorption of ammonia were analyzed.

황화수소 흡착량은 H2S 표준가스로 H2S 10%/N2 90%를 사용하였으며, 유속은 20분간 80 mL를 흘려주고 컬럼직경은 15 mm에 5 g의 흡착제를 채워서 초기공급량과 나중배출량을 측정하여 제거효율로서 흡착되는 양으로 측정하였다.For the hydrogen sulfide adsorption amount, H 2 S 10%/N 2 90% was used as the H 2 S standard gas, and the flow rate was 80 mL for 20 minutes, and the column diameter was 15 mm and filled with 5 g of adsorbent. was measured to measure the adsorbed amount as the removal efficiency.

암모니아 흡착량은 고정층 반응기를 사용하여 암모니아 기체를 반응기 상부에 주입하여 시료층을 거친 후 하부로 배출되도록 하였으며, 흡착 완료 후 하부에서 배출된 암모니아를 휴대용 암모니아 분석장비로 검출하였다. PSA 공정 조건에서 암모니아 흡착을 수행하였으며, PSA는 역압력 레귤레이터(back pressure regulator)를 통해 반응기 내부의 압력을 조절하여 7 bar에서 흡착을 진행하였고, 다시 상압으로 감압시켜 N2를 흘려주며 탈착을 진행하였다.The amount of ammonia adsorption was measured by injecting ammonia gas into the upper part of the reactor using a fixed bed reactor, passing through the sample layer, and then discharging it to the lower part. Adsorption of ammonia was performed under PSA process conditions, and PSA adsorption was performed at 7 bar by adjusting the pressure inside the reactor through a back pressure regulator, and desorption was performed by flowing N 2 by reducing the pressure to normal pressure again. did

그 결과를 하기 표 1에 나타내었다.The results are shown in Table 1 below.

황화수소 제거 효율(%)Hydrogen sulfide removal efficiency (%) 암모니아 흡착량(mmol/g)Ammonia adsorption amount (mmol/g) 실시예 1Example 1 4.94.9 5.05.0 실시예 2Example 2 4.44.4 5.15.1

상기 표 1에 나타낸 바와 같이, 본 발명에 따른 복합 흡착제는 황화수소 제거 및 암모니아 흡착이 가능한 것을 확인할 수 있었다. 특히, 실시예 1의 복합 흡착제의 경우 더욱 높은 황화수소 제거효율을 나타내어 황화수소 제거 및 암모니아 흡착에 사용하기에 바람직한 것으로 판단된다.As shown in Table 1, it was confirmed that the composite adsorbent according to the present invention is capable of removing hydrogen sulfide and adsorbing ammonia. In particular, the composite adsorbent of Example 1 exhibits a higher hydrogen sulfide removal efficiency and is therefore considered preferable for use in removing hydrogen sulfide and adsorbing ammonia.

Claims (3)

커피박을 인산 수용액으로 세척하여 불순물을 제거하는 단계; 불순물이 제거된 커피박을 아염소산나트륨 및 초산을 1:1의 중량비율로 혼합한 혼합용액에 침지하고 25-35℃의 온도에서 80-100분 동안 1차 전처리하는 단계; 1차 전처리된 커피박을 수산화칼륨 수용액에 침지하고 40-50℃의 온도에서 50-70분 동안 2차 전처리하는 단계; 2차 전처리된 커피박을 170-190℃의 온도에서 11-13시간 동안 1차 열처리하는 단계; 1차 열처리된 커피박을 410-430℃의 온도에서 2-4시간 동안 2차 열처리하는 단계; 및 2차 열처리된 커피박을 700-900℃의 온도에서 45-75분 동안 탄화하여 활성탄을 제조하는 단계;를 포함하는 커피박으로부터 활성탄을 제조하는 단계; 및
커피박으로부터 제조된 활성탄 38-42 중량부, 폐흡착제 3-7 중량부, 폐석고분말 7-11 중량부, 수산화철이 함유된 무기성오니 7-11 중량부, 아스코르브산 또는 구연산 2.5-4.5 중량부, 제올라이트 14-18 중량부, 벤토나이트 10-14 중량부 및 수산화칼륨 4.5-6.5 중량부를 혼합하고 350-450℃의 온도에서 열처리하는 단계;를 포함하는 복합 흡착제의 제조방법.Washing the coffee grounds with an aqueous phosphoric acid solution to remove impurities; immersing the coffee grounds from which impurities are removed in a mixed solution of sodium chlorite and acetic acid mixed at a weight ratio of 1:1 and pre-treating at a temperature of 25-35 ° C. for 80-100 minutes; immersing the first pre-treated coffee grounds in an aqueous solution of potassium hydroxide and performing a second pre-treatment at a temperature of 40-50 ° C. for 50-70 minutes; Primary heat treatment of the secondary pre-treated coffee grounds at a temperature of 170-190 ° C. for 11-13 hours; Secondary heat treatment of the first heat-treated coffee waste at a temperature of 410-430 ° C. for 2-4 hours; Preparing activated carbon from coffee waste; and
38-42 parts by weight of activated carbon prepared from coffee waste, 3-7 parts by weight of waste adsorbent, 7-11 parts by weight of waste gypsum powder, 7-11 parts by weight of inorganic sludge containing iron hydroxide, 2.5-4.5 parts by weight of ascorbic acid or citric acid , Mixing 14-18 parts by weight of zeolite, 10-14 parts by weight of bentonite and 4.5-6.5 parts by weight of potassium hydroxide and heat-treating at a temperature of 350-450 ° C. 삭제delete 삭제delete
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KR102599131B1 (en) 2023-02-23 2023-11-07 고등기술연구원연구조합 Method for producing high specific surface area activated carbon using lignocellulosic biomass using resource recycling type advanced activation

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KR890002856A (en) * 1987-07-30 1989-04-11 최근선 Regeneration function control device of V-Cal and its control method
US20030153457A1 (en) * 2000-06-19 2003-08-14 Yasushi Nemoto Adsorbents, process for producing the same, and applications thereof

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Publication number Priority date Publication date Assignee Title
KR890002856A (en) * 1987-07-30 1989-04-11 최근선 Regeneration function control device of V-Cal and its control method
US20030153457A1 (en) * 2000-06-19 2003-08-14 Yasushi Nemoto Adsorbents, process for producing the same, and applications thereof

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KR102599131B1 (en) 2023-02-23 2023-11-07 고등기술연구원연구조합 Method for producing high specific surface area activated carbon using lignocellulosic biomass using resource recycling type advanced activation

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