KR102199410B1 - Adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum-sludge - Google Patents
Adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum-sludge Download PDFInfo
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- KR102199410B1 KR102199410B1 KR1020180173635A KR20180173635A KR102199410B1 KR 102199410 B1 KR102199410 B1 KR 102199410B1 KR 1020180173635 A KR1020180173635 A KR 1020180173635A KR 20180173635 A KR20180173635 A KR 20180173635A KR 102199410 B1 KR102199410 B1 KR 102199410B1
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Abstract
본 발명은, 알럼슬러지 100 중량부에 대하여 산성약품 2~4 중량부와, 금속계 첨가물 0.5~10중량부와, 공정수 50~200중량부를 포함하고, 상기 산성약품은, 폐황산, 재생 황산 또는 공업용 황산(H2SO4), 인산(H3PO4, KH2PO4, K3PO4, K2HPO4), 염산(HCl), 질산(HNO3) 중 어느 하나 또는 둘 이상을 포함하는 것을 특징으로 한다.The present invention includes 2 to 4 parts by weight of an acidic chemical, 0.5 to 10 parts by weight of a metal additive, and 50 to 200 parts by weight of process water, based on 100 parts by weight of alum sludge, and the acidic chemical is waste sulfuric acid, regenerated sulfuric acid or Industrial sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 , KH 2 PO 4 , K 3 PO 4 , K 2 HPO 4 ), hydrochloric acid (HCl), nitric acid (HNO 3 ) of any one or two or more Characterized in that.
Description
본 발명은 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제 및 이의 제조방법에 관한 것으로서, 보다 상세하게는, 알럼계 오니를 재활용하여 화학 흡착능과 물리 흡착능을 동시에 갖도록 물리 화학적 공정을 거쳐 제조된 흡착제가 바이오가스로부터 발생하는 실록산 및 부식성 가스인 황화수소, 암모니아를 동시에 흡착제거할 수 있고, 교체주기가 긴 다공성의 구형(Bead Type) 흡착제를 제공할 수 있으며, 파과된 흡착제는 열처리 및 수증기 개질 처리를 통해 원활하게 재생될 수 있도록 하는 흡착제의 제조방법에 관한 것이다.The present invention relates to an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge and a method for producing the same, and more particularly, an adsorbent manufactured through a physicochemical process to have both chemical adsorption and physical adsorption capability by recycling alum sludge. Siloxane generated from biogas and corrosive gases such as hydrogen sulfide and ammonia can be simultaneously adsorbed and removed, and a porous bead type adsorbent with a long replacement cycle can be provided, and the broken adsorbent can be treated through heat treatment and steam reforming. It relates to a method of manufacturing an adsorbent that enables smooth regeneration.
일반적으로 유기성 폐기물의 재활용 기술 발달에 따라, 음식물 쓰레기(음식물 쓰레기 고형분 및 발생폐수), 가축분뇨, 유기성 슬러지 등과 같은 유기성 폐기물을 이용하여 바이오 가스를 생산하는 기술이 발전되어 왔으며, 바이오 가스는 유기성 폐기물을 혐기성 조건하에서 혐기성 미생물에 의해 발생하게 된다.In general, with the development of recycling technology for organic waste, technology for producing biogas using organic wastes such as food waste (solids and generated wastewater), animal manure, and organic sludge has been developed, and biogas is an organic waste. Is caused by anaerobic microorganisms under anaerobic conditions.
바이오 가스는 주로 메탄(CH4)과 이산화탄소(CO2)가 6:4의 비율로 발생하여 가스엔진, 가스터빈 등과 같은 발전설비에 연료로 공급되어 전기를 생산하거나 보일러에 연료로 공급되어 스팀을 생산하여 소화조 가온이나 건조기의 에너지원으로 사용하고 있다.Biogas mainly generates methane (CH4) and carbon dioxide (CO2) in a ratio of 6:4 and is supplied as fuel to power generation facilities such as gas engines and gas turbines to produce electricity or supplied as fuel to boilers to produce steam. It is used as an energy source for heating digesters or dryers.
그러나 이러한 바이오 가스는 필연적으로 황화수소나 암모니아 및 실록산을 함유하고 있어 문제가 발생된다. 황화수소나 암모니아는 악취를 가진 무색의 유독한 기체이며 발전기나 보일러 등의 설비에 부식을 일으키는 원인물질이 되고, 실록산은 연소 후 SiO2로 산화되어 발전기나 보일러 연소실 내벽에 부착되어 설비의 운전을 방해하여 공정 효율 감소의 원인이 된다.However, such biogas inevitably contains hydrogen sulfide, ammonia, and siloxane, causing problems. Hydrogen sulfide or ammonia is a colorless, toxic gas with an odor and becomes a causative substance for corrosion in facilities such as generators and boilers, and siloxane is oxidized to SiO 2 after combustion and adheres to the inner wall of the combustion chamber of the generator or boiler, interfering with the operation of the facility. As a result, it becomes the cause of reduction in process efficiency.
따라서 바이오 가스를 에너지원으로 사용하기 위해서는 바이오 가스에 함유된 황화수소, 암모니아 및 실록산을 반드시 제거해야만 한다.Therefore, in order to use biogas as an energy source, hydrogen sulfide, ammonia and siloxane contained in biogas must be removed.
건식 탈황, 탈암모니아 설비는 가축분뇨, 음식물 및 유기성 슬러지 등의 혐기성 미생물에 의해 소화반응에 의해 발생하는 소화 가스나 매립장에서 발생하는 매립가스와 같은 바이오 가스를 연료로 사용하여 전기를 발생시키는 발전기나 바이오 가스를 천연가스로 공급하기 위한 고질화 설비에서 바이오 가스 등에 함유된 높은 농도의 황화수소 및 암모니아를 건식방법을 이용해 1개의 흡착탑에서 동시에 제거하기 위한 공정에 사용된다.Dry desulfurization and deammonia facilities are generators or generators that generate electricity by using biogas such as landfill gas or biogas generated by digestion reactions by anaerobic microorganisms such as animal manure, food and organic sludge as fuel. It is used in a process for simultaneously removing high concentrations of hydrogen sulfide and ammonia contained in biogas and the like in one adsorption tower using a dry method in a upgrading facility for supplying biogas as natural gas.
종래에는 소화가스 중에 암모니아를 주로 황산(H2SO4)을 이용한 약액습식으로 제거하고 소화가스 중 수분을 제거하고 건식으로 황화수소를 제거하였다.Conventionally, ammonia in the digestion gas was mainly removed by a chemical liquid wet method using sulfuric acid (H2SO4), moisture in the digestion gas was removed, and hydrogen sulfide was removed by a dry method.
수분을 제거하기 위해 종래에는 워터트랩을 사용하고 있으나 워터트랩은 단순히 응축된 수증기의 방울만을 배출할 뿐 소화가스에 함유되거나 또는 포화상태로 존재하는 수증기를 제거할 수는 없다.Conventionally, a water trap is used to remove moisture, but the water trap simply discharges only droplets of condensed water vapor and cannot remove water vapor contained in the digestive gas or present in a saturated state.
따라서 포화상태의 수증기는 건식 탈황기 내부의 탈황제에 흡수되고 흡수된 수증기는 탈황제와 황화수소의 반응을 방해하며 탈황제의 강도를 약하게 하여 자중에 의한 탈리 및 침착현상을 일으켜 압력손실이 크게 되어 건식탈황기의 효율을 저해할 뿐 아니라 발전기 및 보일러의 운전을 방해하게 된다.Therefore, saturated water vapor is absorbed by the desulfurization agent inside the dry desulfurizer, and the absorbed water vapor interferes with the reaction between the desulfurization agent and hydrogen sulfide, and weakens the strength of the desulfurization agent, causing desulfurization and deposition by its own weight, resulting in a large pressure loss. It not only impairs the efficiency of the system, but also interferes with the operation of the generator and boiler.
이러한 문제를 해결하고자 종래 건식 탈황기는 냉각제습기를 설치하여 냉각방식에 의한 제습을 통해 수증기를 제거하여 왔으며, 냉각방식의 제습에는 불가피하게 열교환기기가 사용되는데 바이오 가스에 함유되어 있는 황화수소 및 암모니아가 강한 부식성 가스여서 열교환기의 튜브에 부식을 발생시켜 열교환기의 수명을 결정적으로 단축시키고 있다.To solve this problem, conventional dry desulfurizers have installed a cooling dehumidifier to remove water vapor through dehumidification by a cooling method, and a heat exchanger is inevitably used for dehumidification of the cooling method. Hydrogen sulfide and ammonia contained in biogas are strong. As it is a corrosive gas, it causes corrosion in the tubes of the heat exchanger, decisively shortening the life of the heat exchanger.
또한 냉각제습기는 냉매가스의 순환으로 냉각효과를 얻고 있기 때문에 이 과정에서 상당한 전력 소모가 불가피한 문제점이 있다.In addition, since the refrigerant dehumidifier obtains a cooling effect through circulation of the refrigerant gas, there is a problem that considerable power consumption is inevitable during this process.
이와 같은 문제점들로 인하여 유지관리비용 상승 및 강산, 강알칼리 폐수처리에 대한 문제점을 동반하게 된다.These problems lead to increased maintenance costs and problems with strong acid and strong alkali wastewater treatment.
또한 종래에는 바이오 가스를 보일러 연료로서 주로 사용하였지만 최근에는 바이오가스를 정제하여 도시가스, 차량충전용가스, 연료전지 등의 용도로까지 사용하고자하기 때문에 고효율을 안정적으로 유지할 수 있는 제습, 탈황설비가 필요하다.In addition, conventionally, biogas was mainly used as a boiler fuel, but recently, since biogas is purified and used for purposes such as city gas, vehicle charging gas, and fuel cells, dehumidification and desulfurization facilities capable of stably maintaining high efficiency are available. need.
본 발명의 배경기술을 알 수 있는 특허로서 특허문헌 1(공개특허공보 제10-2008-0054290호, 분뇨폐기물의 바이오가스를 이용한 발전연료 제조방법 및 이를 이용한 컨테이너형 발전연료 제조장치), 특허문헌 2(등록특허공보 제10-1308405호, 바이오메탄을 이용한 합성 연료 생산 장치 및 방법) 등이 있다.Patent Document 1 (Publication Patent Publication No. 10-2008-0054290, a method for manufacturing power generation fuel using biogas of manure waste, and a container-type power generation fuel manufacturing apparatus using the same) as a patent that can know the background technology of the present invention, Patent Document 2 (Registration Patent Publication No. 10-1308405, Synthetic fuel production apparatus and method using biomethane) and the like.
종래기술에 따른 흡착제는 바이오 가스로부터 황화수소, 암모니아 및 실록산을 동시에 제거할 수 없기 때문에 바이오 가스로부터 황화수소, 암모니아 및 실록산을 단계적으로 제거하기 위한 별도의 공정 및 별도의 흡착제가 요구되므로 황화수소, 암모니아 및 실록산 제거에 소요되는 시간 및 비용을 절감하기 어려운 문제점이 있다.The adsorbent according to the prior art cannot remove hydrogen sulfide, ammonia and siloxane from biogas at the same time, so a separate process for stepwise removal of hydrogen sulfide, ammonia and siloxane from biogas and a separate adsorbent are required, so hydrogen sulfide, ammonia and siloxane There is a problem in that it is difficult to reduce the time and cost required for removal.
또한 한번 사용된 흡착제는 대부분 폐기 처분되어 이를 매립할 시 2차적인 환경문제를 유발할 수 있다.In addition, most of the adsorbents that have been used once are disposed of and disposed of, which may cause secondary environmental problems when landfilling them.
따라서 이를 개선할 필요성이 요청된다.Therefore, there is a need to improve this.
본 발명은 알럼계 오니를 재활용하여 화학 흡착능과 물리 흡착능을 동시에 갖도록 물리/화학적 공정을 거쳐 부식성 가스인 황화수소, 암모니아 및 실록산을 동시에 흡착제거할 수 있고, 교체주기가 긴 다공성의 구형(Bead Type) 흡착제를 제공할 수 있는 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제와, 사용된 흡착제는 열처리 및 수증기 개질 처리를 통해 원활하게 재생될 수 있도록 하는 흡착제의 제조방법을 제공하는데 그 목적이 있다.The present invention is capable of simultaneously adsorbing and removing corrosive gases hydrogen sulfide, ammonia, and siloxane through a physical/chemical process to have both chemical adsorption and physical adsorption capability by recycling alum-based sludge, and a porous spherical shape (Bead Type) with a long replacement cycle It is an object of the present invention to provide an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge capable of providing an adsorbent, and a method for producing an adsorbent that allows the used adsorbent to be smoothly regenerated through heat treatment and steam reforming treatment.
본 발명은, 알럼슬러지 100 중량부에 대하여 산성약품 2~4 중량부와, 금속계 첨가물 0.5~10중량부와, 공정수 50~200중량부를 포함하고, 상기 산성약품은, 폐황산, 재생 황산 또는 공업용 황산(H2SO4), 인산(H3PO4, KH2PO4, K3PO4, K2HPO4), 염산(HCl), 질산(HNO3) 중 어느 하나 또는 둘 이상을 포함하는 것을 특징으로 한다.The present invention includes 2 to 4 parts by weight of an acidic chemical, 0.5 to 10 parts by weight of a metal additive, and 50 to 200 parts by weight of process water, based on 100 parts by weight of alum sludge, and the acidic chemical is waste sulfuric acid, regenerated sulfuric acid or Industrial sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 , KH 2 PO 4 , K 3 PO 4 , K 2 HPO 4 ), hydrochloric acid (HCl), nitric acid (HNO 3 ) of any one or two or more Characterized in that.
또한, 본 발명의 상기 금속계 첨가물은, 산화카드뮴(CdO), 산화구리(CuO), 산화아연(ZnO), 산화납(PbO), 망간 산화물(Mn2O3), 철 산화물(Fe2O3) 중 하나 또는 둘 이상을 포함하는 것을 특징으로 한다.In addition, the metal additives of the present invention are cadmium oxide (CdO), copper oxide (CuO), zinc oxide (ZnO), lead oxide (PbO), manganese oxide (Mn 2 O 3 ), iron oxide (Fe 2 O 3 ) Characterized in that it comprises one or two or more of.
또한, 본 발명의 상기 알럼슬러지 내 상기 금속계 첨가물의 반응 메커니즘은,In addition, the reaction mechanism of the metal additive in the alum sludge of the present invention,
CdO + H2S = CdS + H2OCdO + H 2 S = CdS + H 2 O
CuO + H2S = CuS + H2OCuO + H 2 S = CuS + H 2 O
Fe2O3 + 3H2S = 2Fe2S3 + 3H2OFe 2 O 3 + 3H 2 S = 2Fe 2 S 3 + 3H 2 O
ZnO + H2S = ZnS + H2OZnO + H 2 S = ZnS + H 2 O
Mn2O3 + 3H2S = Mn2S3 + 3H2OMn 2 O 3 + 3H 2 S = Mn 2 S 3 + 3H 2 O
으로 이루어지는 발열반응으로 이루어지는 것을 특징으로 한다.It is characterized by consisting of an exothermic reaction consisting of.
또한, 본 발명은, (a) 알럼슬러지 100 중량부에 대하여 산성약품 2~4 중량부와, 금속계 첨가물 0.5~10중량부와, 공정수 50~200중량부를 포함하는 조성물을 혼합하여 수열 합성하는 단계; (b) 상기 수열 합성하는 단계를 통해 수열 합성된 반응물을 숙성하는 단계; (c) 상기 숙성하는 단계를 거친 숙성물의 함수율을 조절하는 단계; (d) 상기 조절하는 단계를 거친 탈수물을 파쇄하는 단계; (e) 상기 파쇄하는 단계를 거친 파쇄물을 성형하는 단계; (f) 상기 성형하는 단계로 획득한 성형물을 건조하는 단계; (g) 상기 건조하는 단계를 거친 건조물을 탄화하는 단계를 포함하는 것을 특징으로 한다.In addition, the present invention, (a) hydrothermal synthesis by mixing a composition containing 2 to 4 parts by weight of an acidic chemical, 0.5 to 10 parts by weight of a metal additive, and 50 to 200 parts by weight of a process number based on 100 parts by weight of alum sludge. step; (b) aging the reaction product hydrothermally synthesized through the hydrothermal synthesis step; (c) adjusting the moisture content of the aged product that has undergone the aging step; (d) crushing the dehydrated material subjected to the adjusting step; (e) forming the crushed material that has been subjected to the crushing step; (f) drying the molded product obtained by the molding step; (g) It characterized in that it comprises the step of carbonizing the dried product after the drying step.
또한, 본 발명의 상기 (g)단계는, 상기 건조하는 단계를 거친 건조물을 반응기에 넣고 스팀 제너레이터를 통해 발생되는 수증기를 질소 또는 아르곤을 캐리어 가스로 이용하여 상기 반응기에 공급하며, 500~600℃의 온도를 50~120분 동안 유지하여 이루어지고, 한 번 파과되어 회수한 흡착제는 상기 (g)단계 및 상기 (f)단계의 반복을 통해 동일한 황화수소, 암모니아 및 실록산의 흡착능이 재생되는 것을 특징으로 한다.In addition, in the step (g) of the present invention, the dried product, which has undergone the drying step, is put into a reactor, and water vapor generated through a steam generator is supplied to the reactor using nitrogen or argon as a carrier gas, and 500 to 600° C. The adsorbent is recovered by maintaining the temperature of 50 to 120 minutes, and the adsorption capacity of the same hydrogen sulfide, ammonia and siloxane is regenerated through repetition of steps (g) and (f). do.
본 발명에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제 및 이의 제조방법은, 알럼슬러지를 이용해 제조된 흡착제는 공정을 통해 구비된 표면의 활성탄소로 인해 흡착제의 비표면적이 증가하고, 표면의 작용기가 발달하여 황화수소, 암모니아를 제거할 수 있을 뿐 아니라 선형 실록산을 동시에 흡착 제거할 수 있는 이점이 있다.The adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane and its manufacturing method using alum sludge according to the present invention, wherein the adsorbent prepared using alum sludge increases the specific surface area of the adsorbent due to activated carbon on the surface provided through the process, and functional groups on the surface. It has the advantage of being able to remove hydrogen sulfide and ammonia as well as adsorbing and removing linear siloxanes at the same time.
또한, 본 발명에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제 및 이의 제조방법은, 파과된 흡착제가 동일한 탄화 및 수증기 개질 공정을 통해 흡착능이 회복될 수 있는 이점이 있다.In addition, the adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to the present invention and a method for producing the same have an advantage in that the breakthrough adsorbent can recover the adsorption capacity through the same carbonization and steam reforming process.
도 1은 본 발명의 일 실시예에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제의 시험설정서이다.
도 2는 본 발명의 일 실시예에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제의 시험결과이다.
도 3은 본 발명의 일 실시예에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제의 활성화온도, 수증기 공급시간 및 그에 따른 흡착효율이 도시된 그래프이다.1 is a test setup of an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to an embodiment of the present invention.
2 is a test result of an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to an embodiment of the present invention.
3 is a graph showing the activation temperature, water vapor supply time, and adsorption efficiency of the adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to an embodiment of the present invention.
이하, 첨부된 도면들을 참조하여 본 발명에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제 및 이의 제조방법의 일 실시예를 설명한다.Hereinafter, an embodiment of an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to the present invention and a method of manufacturing the same will be described with reference to the accompanying drawings.
이러한 과정에서 도면에 도시된 선들의 두께나 구성요소의 크기 등은 설명의 명료성과 편의상 과장되게 도시되어 있을 수 있다.In this process, thicknesses of lines or sizes of components shown in the drawings may be exaggerated for clarity and convenience of description.
또한, 후술되는 용어들은 본 발명에서의 기능을 고려하여 정의된 용어들로써, 이는 사용자, 운용자의 의도 또는 관례에 따라 달라질 수 있다.In addition, terms to be described later are terms defined in consideration of functions in the present invention, and may vary according to the intention or custom of users or operators.
그러므로 이러한 용어들에 대한 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다.Therefore, definitions of these terms should be made based on the contents throughout the present specification.
도 1은 본 발명의 일 실시예에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제의 시험설정서이고, 도 2는 본 발명의 일 실시예에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제의 시험결과이고, 도 1은 본 발명의 일 실시예에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제의 활성화온도, 수증기 공급시간 및 그에 따른 흡착효율이 도시된 그래프이다.1 is a test setup of an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to an embodiment of the present invention, and FIG. 2 is an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to an embodiment of the present invention. 1 is a graph showing the activation temperature, water vapor supply time, and adsorption efficiency of the adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to an embodiment of the present invention.
도 1 내지 도 3을 참조하면, 본 발명의 일 실시예에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제는, 알럼슬러지 100 중량부에 대하여 산성약품 2~4 중량부와, 금속계 첨가물 0.5~10중량부와, 공정수 50~200중량부를 포함한다.1 to 3, the adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to an embodiment of the present invention includes 2 to 4 parts by weight of an acidic chemical, and 0.5 to metal additives based on 100 parts by weight of alum sludge. 10 parts by weight and 50 to 200 parts by weight of process water are included.
또한, 본 실시예의 흡착제는, 흡착제 표면에 탄화공정으로 생성된 활성탄소가 부생가스에 포함되는 사슬형태(L2~L5)의 실록산을, 알럼슬러지 내부에 생성되는 제올라이트에 고리형(D3~D5)으로 실록산을 흡착 제거하게 된다.In addition, the adsorbent of this embodiment is a chain type (L2 to L5) siloxane in which activated carbon generated by a carbonization process is contained in by-product gas on the surface of the adsorbent, and cyclic (D3 to D5) to zeolite generated inside alum sludge. The siloxane is adsorbed and removed.
본 실시예의 금속계 첨가물은, 산화카드뮴(CdO), 산화구리(CuO), 산화아연(ZnO), 산화납(PbO), 망간 산화물(Mn2O3), 철 산화물(Fe2O3) 중 하나 또는 둘 이상을 포함하고, 알럼슬러지 내 상기 금속계 첨가물의 반응 메커니즘은,The metal additive of this embodiment is one of cadmium oxide (CdO), copper oxide (CuO), zinc oxide (ZnO), lead oxide (PbO), manganese oxide (Mn 2 O 3 ), and iron oxide (Fe 2 O 3 ). Or two or more, and the reaction mechanism of the metal-based additive in alum sludge,
CdO + H2S = CdS + H2OCdO + H 2 S = CdS + H 2 O
CuO + H2S = CuS + H2OCuO + H 2 S = CuS + H 2 O
Fe2O3 + 3H2S = 2Fe2S3 + 3H2OFe 2 O 3 + 3H 2 S = 2Fe 2 S 3 + 3H 2 O
ZnO + H2S = ZnS + H2OZnO + H 2 S = ZnS + H 2 O
Mn2O3 + 3H2S = Mn2S3 + 3H2OMn 2 O 3 + 3H 2 S = Mn 2 S 3 + 3H 2 O
으로 이루어지는 발열반응으로 이루어진다.It consists of an exothermic reaction consisting of.
상기와 같이 구성된 본 발명의 일 실시예에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제 제조방법을 살펴보면 다음과 같다.A method of manufacturing an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to an embodiment of the present invention configured as described above is as follows.
본 발명의 일 실시예에 따른 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제 제조방법은, 알럼슬러지 100 중량부에 대하여 산성약품 2~4 중량부와, 금속계 첨가물 0.5~10중량부와, 공정수 50~200중량부를 포함하는 조성물을 혼합하여 수열 합성하는 단계와, 수열 합성하는 단계를 통해 수열 합성된 반응물을 숙성하는 단계와, 숙성하는 단계를 거친 숙성물의 함수율을 조절하는 단계와, 조절하는 단계를 거친 탈수물을 파쇄하는 단계와, 파쇄하는 단계를 거친 파쇄물을 성형하는 단계와, 성형하는 단계로 획득한 성형물을 건조하는 단계와, 건조하는 단계를 거친 건조물을 탄화하는 단계를 포함한다.The method for preparing an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge according to an embodiment of the present invention includes 2 to 4 parts by weight of an acidic chemical, 0.5 to 10 parts by weight of a metal additive, and process water based on 100 parts by weight of alum sludge. A step of hydrothermal synthesis by mixing a composition containing 50 to 200 parts by weight, a step of aging the reaction product hydrothermally synthesized through a step of hydrothermal synthesis, and a step of adjusting the moisture content of the aged product through the step of aging, and the step of adjusting And crushing the dehydrated product through crushing, shaping the crushed product through the crushing step, drying the molded product obtained by the molding step, and carbonizing the dried product through the drying step.
또한, 본 실시예의 탄화하는 단계는, 건조하는 단계를 거친 건조물을 반응기에 넣고 스팀 제너레이터를 통해 발생되는 수증기를 질소 또는 아르곤을 캐리어 가스로 이용하여 상기 반응기에 공급하며, 500~600℃의 온도를 50~120분 동안 유지하여 이루어진다.In addition, in the carbonizing step of the present embodiment, the dried product, which has undergone the step of drying, is put into the reactor, and water vapor generated through the steam generator is supplied to the reactor using nitrogen or argon as a carrier gas, and a temperature of 500 to 600° C. It is done by holding for 50 to 120 minutes.
1. 수열합성반응.1. Hydrothermal synthesis reaction.
알럼 슬러지는 흡착법에 의한 식수 정제 공정의 부산물이고, 알럼은 식수 정제용으로 가장 일반적으로 사용되는 것으로, 현탁물질과 천연 유기물질을 제거하기 위해 응고제로 첨가되게 된다.Alum sludge is a by-product of the drinking water purification process by the adsorption method, and alum is most commonly used for drinking water purification, and is added as a coagulant to remove suspended substances and natural organic substances.
알럼이 물에 첨가되면, 알럼 슬러지의 하나인 무정형 알루미늄 수산화물이 생성될 수 있고, 알루미늄 수산화물은 다공성 물질이기 때문에 대체로 토양의 개선제나 토양 대체제로 이용되고 있다.When alum is added to water, amorphous aluminum hydroxide, which is one of alum sludge, can be produced, and since aluminum hydroxide is a porous material, it is generally used as a soil improvement agent or soil substitute.
알럼슬러지에는 탈황과 탈암모니아의 기능을 향상시키는 알루미늄(Al)과 규사(Si)가 포함되어 있으며, 알루미늄과 규사를 용출하기 위한 재료로서 산성약품[pH 조절로서, 폐황산, 재생 황산 또는 공업용 황산(H2SO4), 인산(H3PO4, KH2PO4, K3PO4, K2HPO4 등), 염산(HCl), 질산(HNO3) 등 강산, 약산 종류]과 공정수가 사용된다.Alum sludge contains aluminum (Al) and silica sand (Si) that improve the functions of desulfurization and deammonia, and as a material for eluting aluminum and silica sand, acidic chemicals [as pH control, waste sulfuric acid, regenerated sulfuric acid, or industrial sulfuric acid (H2SO4), phosphoric acid (H3PO4, KH2PO4, K3PO4, K2HPO4, etc.), hydrochloric acid (HCl), nitric acid (HNO3) and other strong and weak acids] and process water are used.
본 실시예 에서는 인산과 황산을 예로 들어 설명하며 인산만 사용되는 방법, 인산과 황산이 사용되는 방법이 가능하고, 후자의 경우 먼저 황산으로 처리하고 이어서 인산으로 처리하며 알루미늄과 규사의 용출 조건을 먼저 황산으로 조성한 후 인산으로 후처리함으로써 알루미늄과 규사의 용출량을 높일 수 있다.In this example, phosphoric acid and sulfuric acid are described as examples, and a method using only phosphoric acid and a method using phosphoric acid and sulfuric acid is possible, and in the latter case, first, sulfuric acid is treated, followed by phosphoric acid, and the elution conditions of aluminum and silica sand are first After composition with sulfuric acid, it is possible to increase the elution amount of aluminum and silica by post-treating with phosphoric acid.
산성약품 사용의 일례로 정수 슬러지 100 중량부에 대하여 인산 2~4 중량부, 바람직하게 3 중량부가 혼합되고, 2중량부 미만은 용출량이 적고 4중량부를 초과하면 pH의 급격한 감소로 수열반응기, 교반기 등의 기계류의 부식을 동반할 수 있다.As an example of the use of acidic chemicals, 2 to 4 parts by weight, preferably 3 parts by weight of phosphoric acid are mixed with respect to 100 parts by weight of purified sludge, and less than 2 parts by weight is less eluted, and if it exceeds 4 parts by weight, a hydrothermal reactor, agitator It may be accompanied by corrosion of such machinery.
금속계 첨가물은 산화카드뮴(CdO)과 산화구리(CuO)와 산화아연(ZnO)과 산화납(PbO) 및 이산화망간(MnO2) 중 1개 이상이며, 알럼슬러지 100중량부에 대하여 0.5~1.0중량부가 혼합된다.Metal additives are at least one of cadmium oxide (CdO), copper oxide (CuO), zinc oxide (ZnO), lead oxide (PbO), and manganese dioxide (MnO2), and 0.5 to 1.0 parts by weight are mixed with respect to 100 parts by weight of alum sludge. do.
바람직하게 단독인 경우 1중량부, 2종인 경우 각각 0.5중량부, 3종인 경우 각각 0.33중량부가 사용된다.Preferably, 1 part by weight is used for single, 0.5 parts by weight for each of 2 types, and 0.33 parts by weight for each of 3 types.
금속계 첨가물은 바이오 가스 내 황화수소와 반응하는 촉매제로서 바이오 가스 중에 있는 황화수소 등과 같은 황화합물을 반응 메커니즘을 통해 제거할 수 있다.The metal additive is a catalyst that reacts with hydrogen sulfide in biogas, and can remove sulfur compounds such as hydrogen sulfide in biogas through a reaction mechanism.
공정수는 알럼슬러지 100중량부에 대하여 50~200중량부, 바람직하게 100중량부가 사용되며, 혼합비율은 산성약품의 농도 즉 혼합물의 pH와 관련된 것이다.Process water is used in 50 to 200 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of alum sludge, and the mixing ratio is related to the concentration of the acidic chemical, that is, the pH of the mixture.
상기한 재료(알럼슬러지 100중량부, 황산 0.5중량부, 금속계 첨가물 1중량부, 공정수 100중량부)를 수열반응기에 넣고 상기 수열반응기를 밀폐한 후 반응온도를 80~110℃, 바람직하게 90℃로 유지하고 교반기를 90~110rpm, 바람직하게 100rpm으로 회전하면서 20~40분, 바람직하게 30분간 상기 재료들을 혼합한다.Put the above-described materials (100 parts by weight of alum sludge, 0.5 parts by weight of sulfuric acid, 1 part by weight of metal additives, 100 parts by weight of process water) into a hydrothermal reactor, and seal the hydrothermal reactor, and the reaction temperature is 80 to 110°C, preferably 90 The above materials are mixed for 20 to 40 minutes, preferably 30 minutes while maintaining at °C and rotating the stirrer at 90 to 110 rpm, preferably 100 rpm.
혼합한 혼합물은 pH가 4~5정도로 유지되면서 알루미늄 성분을 용출시키는데 최적의 조건을 가지면서 인산과 반응할 최적을 조건을 가진다.The mixed mixture has the optimum conditions for reacting with phosphoric acid while maintaining the pH at about 4 to 5 and the optimum conditions for eluting the aluminum component.
이어서, 흡착제의 제조를 위하여 인산을 수열반응기에 첨가(알럼슬러지 100중량부에 대하여 인산 3중량부)한다.Subsequently, phosphoric acid is added to a hydrothermal reactor (3 parts by weight of phosphoric acid per 100 parts by weight of alum sludge) to prepare an adsorbent.
수열반응기를 황산 처리 시와 전술한 온도 조건과 교반 조건과 동일하게 조성하고 1시간 30분~2시간 30분간 수열 반응시키고, 온도조건은 80℃ 이하로 유지되면 반응시간이 5시간 이상 소요되어 전기소모와 용기의 과대설계가 이루어지고 110℃ 이상으로 유지되면 공정수의 계속된 공급이 필요하므로 적정의 90℃ 정도로 유지하여 전력낭비 등의 공정을 개선시킬 필요가 있다. 이러한 수열반응을 통해 용출된 알루미늄 성분과 인산의 PO4 -와 반응하여 벌집형의 수열반응물이 제조된다.The hydrothermal reactor is prepared in the same manner as the sulfuric acid treatment and the above-described temperature and stirring conditions, and hydrothermal reaction is carried out for 1 hour 30 minutes to 2 hours 30 minutes. If the temperature condition is kept below 80°C, the reaction time takes 5 hours or more. If consumption and overdesign of the container are made and maintained above 110℃, continuous supply of process water is required. Therefore, it is necessary to improve processes such as power waste by maintaining the appropriate 90℃ level. The aluminum component eluted through this hydrothermal reaction reacts with the PO 4 − of phosphoric acid to produce a honeycomb-type hydrothermal reactant.
2. 저장 및 숙성2. Storage and ripening
전 공정에서 제조된 수열반응물의 숙성 조건은 상온에서 2일, 교반속도 15rpm이며 탈수효율을 증대하기 위한 공정이다.The aging conditions of the hydrothermal reactants prepared in the previous process were 2 days at room temperature, a stirring speed of 15 rpm, and a process to increase dehydration efficiency.
후속 공정인 탈수 공정에서 탈수효율을 높이기 위하여 응집제(고분자 응집제로서 기성품)를 투입할 수 있으며 수열반응물 100중량부에 대하여 0.1~0.2중량부가 사용된다.In the subsequent dehydration process, a coagulant (a ready-made product as a polymer coagulant) can be added to increase the dehydration efficiency, and 0.1 to 0.2 parts by weight is used for 100 parts by weight of the hydrothermal reactant.
3. 탈수.3. Dehydration.
저장 및 숙성을 거친 수열반응물은 함수율이 85~90중량%이며 수분은 탈황과 탈암모니아의 효능을 저하시키므로 탈수기를 통해 수분을 탈수하여 수열반응물의 함수율을 60중량% 이하로 조절한다. 탈수는 필터프레스 등 다양한 제품의 사용이 가능하다.The hydrothermal reactant after storage and aging has a moisture content of 85 to 90% by weight, and moisture decreases the efficacy of desulfurization and deammonia, so the moisture is dehydrated through a dehydrator to adjust the moisture content of the hydrothermal reactant to 60% by weight or less. For dehydration, various products such as filter press can be used.
4. 파쇄.4. Shredding.
탈수를 거친 수열반응물은 건조 전에 일정 입도 바람직하게 2mm 이하로 파쇄된다.The hydrothermal reactant that has undergone dehydration is crushed to a predetermined particle size, preferably 2 mm or less, before drying.
5. 성형.5. Molding.
파쇄 공정을 거친 분말을 직경 10mm 내외의 비드(bead) 형태로 성형하며, 이는 공지의 성형기를 통해 가능하다.The powder that has undergone the crushing process is molded into beads having a diameter of about 10 mm, and this is possible through a known molding machine.
6. 건조.6. Dry.
비드 형태의 성형물을 85~98℃ 온도로 23~25시간 동안 건조하며, 이 건조 조건은 비드 형태로 가공된 성형물을 파괴 없이 수분을 제거하기 위한 조건이다.The bead-shaped molded product is dried for 23 to 25 hours at a temperature of 85 to 98°C, and this drying condition is a condition for removing moisture without destroying the molded product in the bead form.
7. 탄화.7. Carbonization.
이상의 공정을 거치는 중에는 재료들의 특성에 의해 유기물의 산반응에 의한 악취가 발생되며, 장기간 보관 시 수분과 유기물이 반응하여 곰팡이류 등이 발생하므로 흡착제의 기능이 떨어진다.During the above process, an odor occurs due to an acid reaction of organic substances due to the characteristics of the materials, and molds are generated due to the reaction between moisture and organic substances during long-term storage, so the function of the adsorbent decreases.
이와 같이 외부 요인 없이 발생되는 악취를 저감하고 흡착제의 성능을 증대하기 위하여 탄화 공정을 거치게 된다.In this way, a carbonization process is performed in order to reduce odors generated without external factors and increase the performance of the adsorbent.
비드 형태로 가공된 성형물의 탄화 조건은 진공 상태(무산소 분위기, 밀폐 및 질소분위기에서 500~600℃ 온도 및 15~30분, 바람직하게 550℃, 20분이다.)이다.The carbonization conditions of the molded product processed in the form of beads are in a vacuum state (500 to 600°C temperature and 15 to 30 minutes, preferably 550°C and 20 minutes in an oxygen-free atmosphere, airtight and nitrogen atmosphere).
진공 조건에서는 탄화 온도를 적은 에너지로 맞출 수 있는 이점이 있다.In a vacuum condition, there is an advantage that the carbonization temperature can be adjusted with less energy.
탄화 온도와 시간은 서로 밀접한 관계를 맺고 있으며 상기 온도와 시간은 악취의 발생과 곰팡이류 등에 의한 변질을 막고 흡착제를 파괴하지 않으면서 비표면적을 증대하기 위한 범위이다.Carbonization temperature and time are closely related to each other, and the temperature and time are ranges for increasing the specific surface area without destroying the adsorbent and preventing the occurrence of odor and deterioration due to molds.
탄화공정을 행하기 위한 증기 공급장치가 구비된 열처리 장치는, 흡착제의 열처리를 위한 공간이 구비되어 있는 박스형 전기로 형태이다.A heat treatment apparatus equipped with a vapor supply device for performing a carbonization process is in the form of a box-type electric furnace provided with a space for heat treatment of an adsorbent.
전기로 혹은 고정층 반응기의 일면에 발생된 증기와 운반 가스의 유입을 위한 입구와 다른 일면에 파과 흡착제와 반응한 뒤 발생한 가스의 배출을 위한 출구가 갖춰져 있다.An inlet for introducing the vapor and carrier gas generated on one side of the electric furnace or fixed bed reactor and an outlet for discharging the gas generated after reacting with the breakthrough adsorbent are provided on the other side.
증기 공급의 예를 들면, 히팅맨틀 내부에 물을 넣은 2구 둥근 플라스크를 설치하고, 아르곤, 질소 등의 불활성 가스를 운반 가스로 둥근 플라스크 내부로 주입하며, 히팅맨틀의 온도를 조절하여 일정 온도 이상 증가하면 물이 서서히 증발하기 시작하는데, 특정 온도까지 상승시킨 후 1시간동안 공급된 증발수증기량을 계산하여 반응기로 공급된 물의 양을 산출한다.For example of steam supply, a two-neck round flask containing water is installed inside the heating mantle, and inert gases such as argon and nitrogen are injected into the round flask as a carrier gas, and the temperature of the heating mantle is controlled to exceed a certain temperature. When it increases, water slowly begins to evaporate, and the amount of water supplied to the reactor is calculated by calculating the amount of evaporated water vapor supplied for 1 hour after raising to a specific temperature.
이때 증발된 수증기가 반응기 내부에 재응축 되지 않도록 둥근 플라스크로부터 나오는 수증기 관을 히팅밴드 등으로 권선하는 등의 추가 작업이 필요하다.At this time, additional work such as winding the steam pipe from the round flask with a heating band or the like is required to prevent the evaporated steam from recondensing inside the reactor.
이 공정의 목적은, 황화수소 및 암모니아 등의 가스를 산화 처리를 통한 화학반응으로 제거하고, 흡착제의 표면의 탄화를 통해 비표면적을 향상시키며, 수증기 개질을 통해 흡착제 표면에 -COOH, -OH 등의 작용기를 부여하여 H2S및 NH3의 흡착 제거 시 추가적인 효과를 얻고자 함이다.The purpose of this process is to remove gases such as hydrogen sulfide and ammonia through chemical reaction through oxidation treatment, to improve the specific surface area through carbonization of the surface of the adsorbent, and to improve the surface of the adsorbent through steam reforming, such as -COOH and -OH. It is intended to obtain additional effects when adsorbing and removing H 2 S and NH 3 by imparting a functional group.
상기한 제조방법에 의해 제조되는 흡착제에 대한 시험성정서 및 시험결과는 도 1 및 도 2에 도시되었으며, 본 실시예에 따른 흡착제에 의해 황화수소, 암모니아 및 실록산이 동시에 제거됨을 알 수 있다.Test results and test results for the adsorbent prepared by the above manufacturing method are shown in FIGS. 1 and 2, and it can be seen that hydrogen sulfide, ammonia, and siloxane are simultaneously removed by the adsorbent according to the present embodiment.
또한, 도 3에 도시된 그래프는, 1회 사용된 파과 흡착제를 회수한 뒤 탄화공정을 실시한 흡착제에 표면 수증기 개질 시 주요 변수로 열처리 온도 (300~700oC), 투입 수증기량, 열처리 시간 사이의 관계를 나타낸 것이다.In addition, the graph shown in FIG. 3 shows the heat treatment temperature (300 ~ 700 o C), the amount of steam input, and the heat treatment time as the main variables in the surface steam reforming of the adsorbent subjected to a carbonization process after recovering the once-used breakthrough adsorbent. It shows the relationship.
이로써, 알럼계 오니를 재활용하여 화학 흡착능과 물리 흡착능을 동시에 갖도록 물리 화학적 공정을 거쳐 부식성 가스인 황화수소, 암모니아, 실록산을 동시에 흡착제거할 수 있고, 교체주기가 긴 다공성의 구형(Bead Type) 흡착제를 제공할 수 있는 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제 및 이의 제조방법을 제공할 수 있게 된다.Accordingly, it is possible to simultaneously adsorb and remove corrosive gases hydrogen sulfide, ammonia, and siloxane through a physicochemical process to have both chemical adsorption and physical adsorption capability by recycling alum sludge, and a porous bead type adsorbent with a long replacement cycle. It is possible to provide an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge and a method for producing the same.
본 발명은 도면에 도시되는 일 실시예를 참고로 하여 설명되었으나, 이는 예시적인 것에 불과하며, 당해 기술이 속하는 분야에서 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 타 실시예가 가능하다는 점을 이해할 것이다.The present invention has been described with reference to an embodiment shown in the drawings, but this is only exemplary, and various modifications and other equivalent embodiments are possible from those of ordinary skill in the field to which the technology belongs. Will understand.
또한, 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제 및 이의 제조방법을 예로 들어 설명하였으나, 이는 예시적인 것에 불과하며, In addition, an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge and a method of manufacturing the same have been described as an example, but this is only exemplary,
아닌 다른 제품에도 본 발명의 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제 및 이의 제조방법이 사용될 수 있다.In other products, the adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using the alum sludge of the present invention and a method for producing the same may be used.
따라서 본 발명의 진정한 기술적 보호범위는 아래의 특허청구범위에 의해서 정하여져야 할 것이다.Therefore, the true technical protection scope of the present invention should be determined by the following claims.
Claims (5)
상기 산성약품은, 폐황산, 재생 황산 또는 공업용 황산(H2SO4), 인산(H3PO4, KH2PO4, K3PO4, K2HPO4), 염산(HCl), 질산(HNO3) 중 어느 하나 또는 둘 이상을 포함하고,
상기 금속계 첨가물은, 산화카드뮴(CdO), 산화구리(CuO), 산화아연(ZnO), 산화납(PbO), 망간 산화물(Mn2O3), 철 산화물(Fe2O3) 중 하나 또는 둘 이상을 포함하고,
상기 알럼슬러지 내 상기 금속계 첨가물의 반응 메커니즘은,
CdO + H2S = CdS + H2O
CuO + H2S = CuS + H2O
Fe2O3 + 3H2S = 2Fe2S3 + 3H2O
ZnO + H2S = ZnS + H2O
Mn2O3 + 3H2S = Mn2S3 + 3H2O
으로 이루어지는 발열반응으로 이루어지고,
상기 금속계 첨가물 중에 1개의 상기 금속계 첨가물이 포함되는 경우에는 알럼슬러지 100중량부에 대하여 1중량부의 상기 금속계 첨가물이 포함되고,
2종의 상기 금속계 첨가물이 포함되는 경우에는 알럼슬러지 100중량부에 대하여 상기 금속계 첨가물이 각각 0.5중량부씩 포함되고,
3종의 상기 금속계 첨가물이 포함되는 경우에는 알럼슬러지 100중량부에 대하여 상기 금속계 첨가물이 각각 0.33중량부씩 포함되고,
상기 알럼슬러지, 산성약품, 금속계 첨가물 및 공정수를 수열반응기에 넣고 상기 수열반응기를 밀폐한 후 반응온도를 80~110℃로 유지하고, 교반기를 90~110rpm으로 회전하면서 20~40분간 상기 재료들을 혼합하여 수열 합성하여 이루어지는 것을 특징으로 하는 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제.
Including 2 to 4 parts by weight of acidic chemicals, 0.5 to 10 parts by weight of metal additives, and 50 to 200 parts by weight of process water per 100 parts by weight of alum sludge,
The acidic chemicals are waste sulfuric acid, regenerated sulfuric acid or industrial sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 , KH 2 PO 4 , K 3 PO 4 , K 2 HPO 4 ), hydrochloric acid (HCl), nitric acid ( HNO 3 ) contains any one or two or more of,
The metal additive is one or two of cadmium oxide (CdO), copper oxide (CuO), zinc oxide (ZnO), lead oxide (PbO), manganese oxide (Mn 2 O 3 ), and iron oxide (Fe 2 O 3 ). Including the above,
The reaction mechanism of the metallic additive in the alum sludge,
CdO + H 2 S = CdS + H 2 O
CuO + H 2 S = CuS + H 2 O
Fe 2 O 3 + 3H 2 S = 2Fe 2 S 3 + 3H 2 O
ZnO + H 2 S = ZnS + H 2 O
Mn 2 O 3 + 3H 2 S = Mn 2 S 3 + 3H 2 O
It consists of an exothermic reaction consisting of,
When one metal additive is included in the metal additive, 1 part by weight of the metal additive is included with respect to 100 parts by weight of alum sludge,
When the two kinds of metal additives are included, 0.5 parts by weight of each of the metal additives is included with respect to 100 parts by weight of alum sludge,
When the three kinds of metal additives are included, 0.33 parts by weight of each of the metal additives are included with respect to 100 parts by weight of alum sludge,
Put the alum sludge, acidic chemicals, metal additives, and process water into a hydrothermal reactor, seal the hydrothermal reactor, maintain the reaction temperature at 80 to 110°C, and rotate the agitator at 90 to 110 rpm for 20 to 40 minutes. Adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge by mixing and hydrothermal synthesis.
(b) 상기 수열 합성하는 단계를 통해 수열 합성된 반응물을 숙성하는 단계;
(c) 상기 숙성하는 단계를 거친 숙성물의 함수율을 조절하는 단계;
(d) 상기 조절하는 단계를 거친 탈수물을 파쇄하는 단계;
(e) 상기 파쇄하는 단계를 거친 파쇄물을 성형하는 단계;
(f) 상기 성형하는 단계로 획득한 성형물을 건조하는 단계;
(g) 상기 건조하는 단계를 거친 건조물을 탄화하는 단계를 포함하고,
상기 (g)단계는, 상기 건조하는 단계를 거친 건조물을 반응기에 넣고 스팀 제너레이터를 통해 발생되는 수증기를 질소 또는 아르곤을 캐리어 가스로 이용하여 상기 반응기에 공급하며, 500~600℃의 온도를 50~120분 동안 유지하여 이루어지고,
한 번 파과되어 회수한 흡착제는 상기 (g)단계 및 상기 (f)단계의 반복을 통해 동일한 황화수소, 암모니아 및 실록산의 흡착능이 재생되고,
상기 (a)단계는,
상기 금속계 첨가물 중에 1개의 상기 금속계 첨가물이 포함되는 경우에는 알럼슬러지 100중량부에 대하여 1중량부의 상기 금속계 첨가물이 포함되고,
2종의 상기 금속계 첨가물이 포함되는 경우에는 알럼슬러지 100중량부에 대하여 상기 금속계 첨가물이 각각 0.5중량부씩 포함되고,
3종의 상기 금속계 첨가물이 포함되는 경우에는 알럼슬러지 100중량부에 대하여 상기 금속계 첨가물이 각각 0.33중량부씩 포함되고,
상기 알럼슬러지, 산성약품, 금속계 첨가물 및 공정수를 수열반응기에 넣고 상기 수열반응기를 밀폐한 후 반응온도를 80~110℃로 유지하고, 교반기를 90~110rpm으로 회전하면서 20~40분간 상기 재료들을 혼합하여 수열 합성하여 이루어지는 것을 특징으로 하는 알럼슬러지를 이용하는 황화수소 암모니아 실록산 동시제거용 흡착제 제조방법.(a) hydrothermal synthesis by mixing a composition comprising 2 to 4 parts by weight of an acidic chemical, 0.5 to 10 parts by weight of a metal additive, and 50 to 200 parts by weight of process water based on 100 parts by weight of alum sludge;
(b) aging the reaction product hydrothermally synthesized through the hydrothermal synthesis step;
(c) adjusting the moisture content of the aged product that has undergone the aging step;
(d) crushing the dehydrated material subjected to the adjusting step;
(e) molding the crushed material that has been subjected to the crushing step;
(f) drying the molded product obtained by the molding step;
(g) carbonizing the dried product that has been subjected to the drying step,
In the step (g), the dried product, which has undergone the drying step, is put into a reactor, and water vapor generated through a steam generator is supplied to the reactor using nitrogen or argon as a carrier gas, and a temperature of 500 to 600°C is 50 to Is achieved by holding for 120 minutes,
The adsorbent once broken through and recovered is regenerated with the same adsorption capacity of hydrogen sulfide, ammonia and siloxane through repetition of steps (g) and (f),
The step (a),
When one metal additive is included in the metal additive, 1 part by weight of the metal additive is included with respect to 100 parts by weight of alum sludge,
When the two kinds of metal additives are included, 0.5 parts by weight of each of the metal additives is included with respect to 100 parts by weight of alum sludge,
When the three kinds of metal additives are included, 0.33 parts by weight of each of the metal additives are included with respect to 100 parts by weight of alum sludge,
Put the alum sludge, acidic chemicals, metal additives, and process water into a hydrothermal reactor, seal the hydrothermal reactor, maintain the reaction temperature at 80 to 110°C, and rotate the agitator at 90 to 110 rpm for 20 to 40 minutes. A method for producing an adsorbent for simultaneous removal of hydrogen sulfide ammonia siloxane using alum sludge by mixing and hydrothermal synthesis.
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