KR101979343B1 - Adsorbent for acid exhaust gas removal and its manufacturing method - Google Patents
Adsorbent for acid exhaust gas removal and its manufacturing method Download PDFInfo
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
본 발명은 화학공정에서 발생되는 산성가스 또는 반도체 제조 공정 중 etching 공정에서 배출되는 산 배기가스 (AlCl3, BCl3, Cl2, HCl, HF) 등을 제거를 위해 유용하게 사용될 수 있다. 본 흡착제는 Ni/Cu/Zn 수산화물, 탄산암모늄, 수산화알루미늄 그리고 규조토 등으로 구성되어 있다. 산 배기가스 제거용 흡착제의 양산 및 제품화를 위해 다양한 성형 방법을 설계하였으며 검토 결과 1.0 ~ 5.0 mm 직경 크기의 흡착 또는 반응의 펠렛 형태의 압출 방법으로 제조할 수 있다. CT-150에 의한 산 배기가스 처리의 핵심 기술은 Cu, Ni, Zn 착염의 반응 참여이다. 이상과 같은 방법으로 반응물은 상온 ~ 150℃ 구간에서 건조되고 필요 시 250℃까지 소성할 수 있다.The present invention can be advantageously used for removing acid gas generated in a chemical process or acid exhaust gas (AlCl 3 , BCl 3 , Cl 2 , HCl, HF) discharged from an etching process during a semiconductor manufacturing process. The adsorbent consists of Ni / Cu / Zn hydroxide, ammonium carbonate, aluminum hydroxide and diatomaceous earth. Various molding methods have been designed for mass production and commercialization of adsorbents for removing exhaust gases. As a result, adsorption or reaction pellet-shaped extrusion methods with diameters of 1.0 to 5.0 mm can be manufactured. The core technology of acid exhaust treatment by CT-150 is the reaction of Cu, Ni, and Zn complexes. In the same manner as above, the reactants are dried at a temperature ranging from room temperature to 150 ° C and can be calcined up to 250 ° C if necessary.
Description
본 발명은 반도체 공정에서 배출되는 산 배기가스를 효율적으로 처리할 수 있는 흡착제에 관한 것이며, 보다 구체적으로 본 발명에 따른 산 배기가스 처리 반응의 주요 기술적 구성은 전이금속의 암모니아 착염과 요소의 반응참여에 있으며, Zn, Ni 혹은 Cu의 수산화물을 탄산암모늄, 규조토, 수산화 알루미늄을 소정의 중량%로 혼합하여 펠렛 1.0 ~ 5.0 mm 크기로 압출 성형하여 제조된 산 배기가스 흡착제에 관한 것이다.The present invention relates to an adsorbent capable of efficiently treating acid exhaust gas discharged from a semiconductor process, and more particularly, the present invention relates to an acid exhaust gas treatment reaction according to the present invention in which ammonia complexation of a transition metal and reaction The present invention relates to an acid exhaust gas adsorbent produced by mixing hydroxide of Zn, Ni or Cu with ammonium carbonate, diatomaceous earth or aluminum hydroxide at a predetermined weight% and extruding the pellets to a size of 1.0 to 5.0 mm.
반도체 제조 공정에서 배출되는 배기가스에는 미반응된 독성 가스와 유해한 반응 생성물이 많이 포함되고 있어 이것을 처리시키지 않고 외부에 배출하는 것은 매우 위험하므로 중화 처리하여 배출하여야 한다.The exhaust gas emitted from the semiconductor manufacturing process contains unreacted toxic gas and harmful reaction products. Therefore, it is very dangerous to discharge the exhaust gas to the outside without treating it. Therefore, the exhaust gas should be neutralized and discharged.
종래의 방법은 습식법, 흡착법, 소각법 등이 사용되었다. 흡착법은 주로 수산화물을 이용하여 화학반응으로 처리해 왔다Conventional methods include a wet method, an adsorption method, and an incineration method. The adsorption process has mainly been treated with chemical reactions using hydroxides
종래에 화학 흡착법을 사용하는 것으로 산화철 또는 수산화철을 사용한 반응식은 다음과 같다.The reaction formula using iron oxide or iron hydroxide in the prior art using the chemical adsorption method is as follows.
산화철: Fe2O3 + 6HCl 2FeCl3 + 3H2OIron oxide: Fe 2 O 3 + 6HCl 2FeCl 3 + 3H 2 O
수산화철: Fe(OH)3 + 3HCl FeCl3 + 3H2OIron hydroxide: Fe (OH) 3 + 3HCl FeCl 3 + 3H 2 O
본 방법에서 정의하는 전이금속의 암모니아 착염반응은 다음과 같다.The ammonia complexation reaction of the transition metal as defined in the present method is as follows.
Zn(NH3)4(OH)2 + 6HCl ZnCl3 + 4NH3Cl + H2OZn (NH 3 ) 4 (OH) 2 + 6HCl ZnCl 3 + 4NH 3 Cl + H 2 O
상기 반응식을 비교해 보면 종래의 수산화철을 사용하는 것보다 암모니아 착염을 사용할 경우, HCl의 처리량이 2배 증가됨을 알 수 있다.Comparing the above reaction formulas, it can be seen that the amount of HCl to be treated is doubled when ammonia complex salt is used rather than using conventional iron hydroxide.
여기에서 전이금속으로 Zn 을 대신하여 Ni, Cu, Co 등이 사용될 수 있다.Here, Ni, Cu, Co, or the like may be used as a transition metal instead of Zn.
활성탄을 사용하는 경우에는 싸고 간단한 점이 장점이나 장치의 부피가 크고, 화재의 위험과 반응 후 나오는 고온의 독성 및 반응성이 강한 기체를 제거하기에는 한계가 있다.In the case of using activated carbon, it is cheap and simple, but has a large volume of apparatus, and there is a limit to remove a gas having a high toxicity and reactivity at a high temperature after a fire and a reaction.
또한 활성탄 교체 시 분진이 발생하는 문제점이 있다.Also, there is a problem that dust is generated when the activated carbon is replaced.
고온을 이용하여 태우는 방법도 사용되지만 LPG와 같은 폭발성 연료를 취급해야 하며 안전 등의 유지에 많은 주의가 필요하며, 계속 고온을 유지해야 하므로 운영비가 많이 소요되고, 고온 반응에 의한 또 다른 독성 부산물이 발생될 수 있다.However, it is necessary to treat explosive fuel such as LPG, and it is necessary to pay attention to the maintenance of safety, etc., and it is necessary to keep the high temperature continuously. Therefore, the operation cost is high and another toxic by- Lt; / RTI >
물을 사용하는 습식법은 장치가 커서 설치 공간이 많이 필요하고 다량의 폐수를 발생시키는 단점이 있다.The wet method using water has a disadvantage in that it requires a large installation space and a large amount of waste water.
수분이 역류하는 경우에는 전체 공정을 오염 시켜서 반응기에서 원하지 않는 반응을 일으키기도 하며, 반응기를 오염시키며, 생산품의 품질을 떨어뜨리며, 오염과 부산물 처리 때문에 고가의 장비를 수리해야 하고 진공 펌프가 정지되기도 하여, 고가의 제품을 생산하는 시설을 중지시키기도 한다.If water is countercurrent, it will contaminate the entire process, causing unwanted reactions in the reactor, polluting the reactor, reducing the quality of the product, repairing expensive equipment due to contamination and byproducts, and shutting off the vacuum pump Thereby stopping facilities that produce expensive products.
이러한 만약의 막대한 손실 때문에 가능하면 물을 이용한 산 배기가스의 제거는 피하는 경향이 있다.Because of this enormous loss, it tends to avoid the removal of acid exhaust using water if at all possible.
그래서 최근에는 화학 흡착법을 이용한 건식법으로 산 배기가스를 제거하는 방법(dry scrubber)으로 많이 바뀌고 있는 실정이다.In recent years, dry scrubbing has been widely used as a method of removing exhaust gas by a dry chemical method using a chemical adsorption method.
반도체 및 평판 디스플레이 제조공정에서 사용되고 발생하는 공정가스들은 대부분 할로겐 계 산 배기가스가 주를 이루는데, 이중 일부는 폭발성 가스로써 물리적 흡착이 아닌 화학적 반응에 의한 화학적 흡착을 이용하여 흡착 처리한다.Most of the process gases used and generated in the semiconductor and flat panel display manufacturing process are mostly halogen-based exhaust gases, some of which are adsorbed by chemical adsorption by chemical reaction rather than physical adsorption as an explosive gas.
화학적 흡착제거에 사용되는 물질로 금속수산화물이 사용되는데, 이는 상기 공정가스와 반응하여 화학적 흡착에 의해 안전하게 흡착처리 할 수 있다.The metal hydroxide is used as a substance to be used for chemical adsorption elimination, which can be adsorbed safely by chemical adsorption in reaction with the process gas.
따라서 흡착제를 설계 시 공정가스와의 발열반응을 최대한 억제함과 더불어 각각의 공정가스와 금속수산화물 흡착제의 반응 메커니즘을 통해 최대의 흡착용량을 가지며, 안전하게 처리할 수 있도록 설계하는 것이 핵심이다.Therefore, it is essential to design the adsorbent to minimize the exothermic reaction with the process gas when designing the adsorbent, and to maximize the adsorption capacity through the reaction mechanism of each process gas and the metal hydroxide adsorbent, and to design the process safely.
본 발명과 관련된 종래기술로 대한민국 공개특허공보 제특1991-0005918호에는 천연 제올라이트를 산과 수산화나트륨 용액으로 처리한 후 암모니아수나 암모늄염 용액으로 처리하고 가열하여 활성화 시킴을 특징으로 하는 천연 제올라이트를 이용한 흡착제가 개시되어 있고, 대한민국 공개특허공보 제특1992-7003198호에는 흡착제조성물 및 그것을 제조하는 방법이 개시되어 있으나, 본 발명에 따른 전이금속산화물 또는 전이금속수산화물이 암모니아 착염물을 혼합 반죽하여 압출 성형하여 제조된 산 배기가스 제거를 위한 흡착제와는 조성물 성분, 기술적 구성 및 기술적 과제 등에서 차이가 현저하다.In the prior art related to the present invention, Korean Patent Laid-Open Publication No. 1991-0005918 discloses an adsorbent using natural zeolite characterized in that natural zeolite is treated with an acid and a sodium hydroxide solution, followed by treatment with ammonia water or ammonium salt solution and heating to activate the natural zeolite. Korean Patent Laid-Open Publication No. 1992-7003198 discloses an adsorbent composition and a method for producing the same. However, the transition metal oxide or transition metal hydroxide according to the present invention is not limited to the acid produced by extrusion molding the ammonia- And the composition, technical composition, and technical problems of the adsorbent for exhaust gas removal are remarkable.
본 발명이 해결하려는 과제는 산 배기가스를 제거하기 위해 흡착제를 제조하되, 반응 효율이 우수한 흡착제를 제조하고, 표면적을 크게 하여 반응 효율을 높이는데 있다.A problem to be solved by the present invention is to prepare an adsorbent for eliminating acid exhaust gas, to prepare an adsorbent excellent in reaction efficiency, and to increase the reaction efficiency by increasing the surface area.
본 발명이 해결하려는 또 다른 과제는 흡착과 확산 그리고 반응이 용이한 입자의 제조와 화학적 흡착이 쉬운 하이드로 옥사이드(hydroxide) 형태의 금속을 사용하고 최대한 많은 반응물을 흡수하고 분산시킬 수 있는 담체를 선정하는데 있다.Another problem to be solved by the present invention is to select a carrier capable of adsorbing and dispersing as many reactants as possible using a hydroxide type metal which is easy to adsorb, have.
즉, 결정성과 다공성 그리고 비표면적이 뛰어난 담체의 선정이 고려됨으로써 다양한 결정 구조로 인한 흡착과 확산, 반응성이 용이하고 화학적 흡착으로 폭발이나 화재의 염려가 없으며 금속 하이드로 옥사이드(hydroxide)가 암모니아 착염이 이루어지면서 다양한 구조를 가진 입자의 생성이 용이하여 활성점의 극대화를 발생시키는데 있다.In other words, it is easy to adsorb, diffuse, and react due to various crystal structures, considering the selection of carrier having excellent crystallinity, porosity and specific surface area. There is no fear of explosion or fire due to chemical adsorption, and metal hydroxide It is easy to generate particles having various structures, thereby maximizing the active points.
본 발명 과제의 해결 수단은 산 배기가스를 처리하기 위하여 Ni 혹은 Cu의 수산화물과 암모니아 착염을 위한 탄산암모늄 및/또는 암모니아수와 다공성을 가지면서 화재 및 폭발성이 없는 규조토와 수산화알루미늄을 소정의 중량%로 혼합하여 펠렛 1.0 ~ 5.0 mm 크기로 압출 성형하여 제조된 산 배기가스 흡착제를 제공하는데 있다.The object of the present invention is to provide a method for treating acid exhaust gas, comprising the steps of: hydrolyzing Ni and / or Cu, ammonium carbonate and / or ammonia water for ammonia complexation, and diatomaceous earth having porosity, And then extruding the pellets to a size of 1.0 to 5.0 mm to provide an acid exhaust gas adsorbent.
본 발명의 또 다른 과제의 해결 수단은 탄산암모늄의 중량을 4% ~ 23% 으로 하고 수산화알루미늄의 중량을 1% ~ 9% 으로 하고 요소의 중량을 10% ~ 38% 으로 혼합 반죽하여 성형 제조된 산 배기가스 흡착제를 제공하는데 있다.A further object of the present invention is to provide a method for producing a molded article which is produced by mixing and kneading the weight of the urea at 10% to 38% with the weight of the ammonium carbonate being 4% to 23%, the weight of the aluminum hydroxide being 1% And to provide an acid exhaust gas adsorbent.
본 발명의 또 다른 과제의 해결 수단은 제올라이트와 규조토 담체에 Cu, Ni 혹은 Zn 수산화물, 탄산암모늄 및/또는 암모니아수, 바인더인 수산화알루미늄을 혼합하여 성형 제조된 산 배기가스 흡착제를 제공하는데 있다.Another object of the present invention is to provide an acid exhaust gas adsorbent formed by mixing zeolite and a diatomaceous earth carrier with Cu, Ni or Zn hydroxide, ammonium carbonate and / or ammonia water and aluminum hydroxide as a binder.
본 발명의 또 다른 과제의 해결 수단은 건조 조건을 드라이 오븐 40℃ 내지 50℃ 에서 90분, 300분 그리고 상온 건조하여 성형 제조된 산 배기가스 흡착제를 제공하는데 있다.A further object of the present invention is to provide an acid exhaust gas adsorbent formed by drying a drying condition at 40 to 50 DEG C for 90 minutes, 300 minutes and at room temperature in a dry oven.
본 발명은 산 배기가스를 제거하기 위해 결정성과 다공성과 비표면적이 뛰어난 규조토를 사용함으로써 다양한 결정 구조로 인한 흡착과 확산, 반응성이 용이하고 화학적 흡착으로 폭발이나 화재의 염려가 없어 안정한 흡착제를 제조할 수 있는 효과가 있다.The present invention uses a diatomaceous earth having excellent crystallinity, porosity and specific surface area to remove acid exhaust gas, thereby making it easy to adsorb, diffuse, and react due to various crystal structures, and to produce a stable adsorbent without any fear of explosion or fire due to chemical adsorption There is an effect that can be.
본 발명의 또 다른 효과는 Ni, Cu, Zn 수산화물이 암모니아 착염이 이루어지면서 다양한 구조를 가진 입자의 생성이 용이하며 반응시 흡착 효율이 우수하며 활성점의 극대화를 보이는 등의 상승된 효과가 있다.Another effect of the present invention is that the Ni, Cu, and Zn hydroxides are easily complexed with ammonia to produce particles having various structures, and the adsorption efficiency during the reaction is excellent and the active sites are maximized.
도 1은 본 발명의 따른 산 배기가스 흡착제의 제조 방법의 기본 흐름도이다.1 is a basic flowchart of a method for producing an acid exhaust gas adsorbent according to the present invention.
본 발명을 실시하기 위한 구체적인 내용에 대하여 살펴본다.Hereinafter, the present invention will be described in detail.
본 발명은 전이금속과, 높은 다공성을 가지면서 화재나 폭발의 위험성이 없는 규조토와, 암모니아 착염 및 바인더를 소정 비율로 혼합 반죽하여 1.0 ~ 5.0 mm 직경을 가진 펠렛 형상으로 압출기를 이용하여 성형 제작된 산 배기가스 제거를 위한 흡착제이다. The present invention relates to a method for producing a molded article, which comprises a transition metal, a diatomaceous earth having high porosity and no risk of fire or explosion, ammonia complex salt and binder in a predetermined ratio and kneading and kneading the mixture into a pellet having a diameter of 1.0 to 5.0 mm It is an adsorbent for removing acid exhaust gas.
본 발명의 명세서 상의 흡착제와 반응 흡착제는 용이한 이해를 위하여 동일한 의미로 혼용 사용되었다. The adsorbents and reaction adsorbents described in the present invention have been used interchangeably for the sake of easy understanding.
상기 펠렛 크기를 상기 한정한 수치를 벗어나 제작할 수 있고, 그 형상도 다양하게 성형 제작할 수 있다. 본 발명에 따른 구체적인 실시 예를 살펴본다.The pellet size can be produced outside of the above-described defined values, and the shape of the pellet can be variously formed and manufactured. A specific embodiment according to the present invention will be described.
<실시 예><Examples>
본 발명에 따른 구체적인 기술적 구성을 살펴본다. A detailed technical configuration according to the present invention will be described.
본 발명에 따른 흡착제가 상승된 효과를 가지는 원리를 살펴보면, 전이금속의 암모니아 착염반응은 다음과 같다.The ammonia complexing reaction of the transition metal is as follows.
Zn(NH3)4(OH)2 + 6HCl ZnCl3 + 4NH3Cl + H2OZn (NH 3 ) 4 (OH) 2 + 6HCl ZnCl 3 + 4NH 3 Cl + H 2 O
상기 반응식을 비교해 보면 앞서 종래 기술에서 수산화철을 이용한 반응보다 암모니아 착염을 사용할 경우, HCl의 처리량이 2배 증가됨을 알 수 있다.Comparing the above reaction formulas, it can be seen that the amount of HCl is doubled when the ammonia complex salt is used rather than the reaction using the iron hydroxide in the prior art.
여기에서 전이금속으로 Zn 을 대신하여 Ni, Cu, Co 등이 사용될 수 있다.Here, Ni, Cu, Co, or the like may be used as a transition metal instead of Zn.
본 발명에 따른 산 배기가스 제거를 위한 흡착제의 구체적인 제조 방법을 살펴본다. A specific method for producing an adsorbent for removing acid exhaust gas according to the present invention will be described.
전이금속으로 금속수산화물의 원료인 Ni/Cu 슬러지와, NH3 소스인 암모니아수 및/또는 탄산암모늄을 적정량 혼합 교반하여 적당한 수분을 함유한 혼합물 형태로 반죽하는 단계를 포함한다.Mixing the Ni / Cu sludge as a transition metal as a raw material of the metal hydroxide with ammonia water and / or ammonium carbonate as an NH 3 source in an appropriate amount and stirring and kneading the resulting mixture into a mixture containing an appropriate amount of water.
다음은 반죽된 혼합물에 높은 다공성을 가지면서 화재 및 폭발의 위험이 없는 규조토 담체와, 바인더인 수산화알루미늄을 적정량 넣어서 혼합물을 교반하여 흡착제를 성형 제조할 수 있는 상태로 반죽하는 단계를 포함한다. 반죽의 상태는 통상의 흡착제를 압출기로 성형 제작할 때 유지하는 반죽 상태, 즉 압출 성형하기 적당한 점도와 함수율로 반죽하면 된다.Next, the kneaded mixture includes a diatomaceous carrier having high porosity and no risk of fire and explosion, and an appropriate amount of aluminum hydroxide as a binder, and stirring the mixture to knead the mixture in a state capable of forming an adsorbent. The state of the dough may be kneaded in a kneading state in which an ordinary adsorbent is retained when the kneaded product is molded by an extruder, that is, a suitable viscosity and water content for extrusion molding.
반죽된 혼합물을 압출기를 이용하여 펠렛 형상으로 압출 성형하는 단계를 포함한다.And extruding the kneaded mixture into pellets using an extruder.
상기 산 배기가스 제거를 위한 흡착제의 제조 방법에서, 금속수산화물(Ni/Cu 등의 슬러지)와 NH3 소스인 암모니아수 또는 탄산암모늄을 적정량 혼합 교반하여 적당한 수분을 함유한 혼합물 형태로 반죽한 후, 담체인 규조토와 바인더인 수산화알루미늄을 적정량 넣어서 혼합물을 교반기로 반죽하여 혼합물을 제조하거나, 동시에 필요한 조성물을 모두 넣어서 교반기로 교반하여 반죽할 수도 있다. In the method for producing an adsorbent for removing the acid exhaust gas, a metal hydroxide (sludge such as Ni / Cu), ammonia water as an NH 3 source or ammonium carbonate is mixed and stirred in an appropriate amount to form a mixture containing an appropriate amount of water. The diatomite and aluminum hydroxide as binders may be added in an appropriate amount, and the mixture may be kneaded with an agitator to prepare a mixture, or all necessary components may be added at the same time, followed by kneading with a stirrer.
펠렛은 1.0 ~ 5.0 mm 직경 또는 크기를 가지며, 구형 또는 원통형을 포함한 다양한 형상으로 제조될 수 있다.The pellets have a diameter or size of 1.0 to 5.0 mm and can be manufactured in various shapes including spherical or cylindrical.
1.0 ~ 5.0 mm 직경 또는 크기의 펠렛은 구형인 경우에 직경을 나타내고, 원통형인 경우에는 원통의 직경과 원통의 길이를 나타내는 수치이며, 정육면체와 직육면체의 경우에는 가로, 세로 및 높이의 길이를 나타낸다. The pellets of 1.0 to 5.0 mm in diameter or size have a diameter in the case of a spherical shape, numerical values indicating the diameter of the cylinder and the length of the cylinder in the case of a cylindrical shape, and the lengths of the height, width and height in the case of a cube and a rectangular parallelepiped.
성형된 약제는 드라이 오븐에서 건조 또는 상온 건조하는 단계를 거쳐서 본 발명에 따른 흡착제가 제조 완료된다. 상기 드라이 오븐의 온도를 25℃ 에서 150℃까지에서 설정된 온도로 유지하여 건조시킬 수 있다.The formed medicament is dried in a dry oven or dried at room temperature to complete the adsorbent according to the present invention. The temperature of the dry oven may be maintained at a set temperature from 25 ° C to 150 ° C to dry.
필요에 따라, 250℃ 내외에서 소성시키는 단계를 더 포함할 수도 있다. If necessary, it may further include a step of calcining at about 250 ° C.
본 발명에 따른 산 배기가스 제거를 위한 흡착제의 조성물에 의한 본 발명의 보호 범위를 살펴본다.The scope of protection of the present invention by the composition of the adsorbent for removing acid exhaust gas according to the present invention will be described.
본 발명은 앞서 반응식에서와 같이 반응효율을 높이기 위하여 전이금속산화물 또는 전이금속수산화물이 암모니아와 착염물을 형성하여 제조된 산 배기가스 제거를 위한 흡착제이다.The present invention is an adsorbent for eliminating acid exhaust gas prepared by forming a transition metal oxide or a transition metal hydroxide with ammonia to increase the reaction efficiency as in the above reaction formula.
본 발명의 또 다른 기술적 구성은 전이금속으로 Cu, Ni, Zn, Co 중에서 1가지 이상을 선택하여 중량비 5% ~ 60%를 주입하여 암모니아와 착염물을 형성하여 압출 성형 제조된 산 배기가스 제거를 위한 흡착제이다. In another technical construction of the present invention, at least one of Cu, Ni, Zn, and Co is selected as a transition metal, and 5 to 60% by weight of the transition metal is injected to form ammonia and a complex salt. Lt; / RTI >
본 발명의 또 다른 기술적 구성으로 암모니아의 원료로는 암모니아수(NH4OH), 탄산암모늄((NH4)2CO3), 요소((NH2)2CO) 및 중탄산암모늄(NH4HCO3) 중에서 하나 이상을 선택하여 중량비 5% ~ 60%를 주입하여 전이금속산화물 또는 전이금속수산화물과 암모니아 착염물을 형성하여 제조된 산 배기가스 제거를 위한 흡착제이다.Ammonia water (NH 4 OH), ammonium carbonate ((NH 4 ) 2 CO 3 ), urea ((NH 2 ) 2 CO) and ammonium bicarbonate (NH 4 HCO 3 ) as raw materials for ammonia, , And then injecting 5 to 60% by weight of the transition metal oxide or transition metal hydroxide to form an ammonia complex salt.
본 발명에 따른 산 배기가스 제거를 위한 흡착제를 제조하기 위한 바인더 및 담체로써 규소 화합물(산화물 또는 수산화물), 천연제올라이트, 활성알루미나, 수산화알루미늄, 규조토 중에서 하나 이상을 선택하여 중량비 1% ~ 50%를 혼합 사용하는 제조된다.At least one of a silicon compound (oxide or hydroxide), natural zeolite, activated alumina, aluminum hydroxide and diatomaceous earth is selected as a binder and a carrier for preparing an adsorbent for removing acid exhaust gas according to the present invention, and a weight ratio of 1% to 50% Mixed is manufactured using.
규조토의 경우에는 담체와 바인더 역할을 동시하며, 보다 견고한 바인더는 수산화알루미늄이다. 상기 바인더와 담체의 중량비 1% ~ 50% 중에서 수산화알루미늄을 전체 흡착제 중량% 중 1% ~ 9% 으로 혼합함이 바람직하다. In the case of diatomaceous earth, it acts as a carrier and binder, while the harder binder is aluminum hydroxide. Aluminum hydroxide is preferably mixed in an amount of 1% to 9% by weight of the total adsorbent in a weight ratio of 1% to 50% of the binder and the carrier.
그래서 본 발명의 조성물의 혼합비를 기재할 때 바인더와 담체를 묶어서 기재한 것이다.Thus, when describing the mixing ratio of the composition of the present invention, the binder and the carrier are described by binding.
본 발명에 따른 산 배기가스 제거를 위한 흡착제의 조성물의 조성비는 전이금속을 10중량% ~ 80 중량%로 주입하고, 암모니아 조성물을 10중량% ~ 30 중량% 로 주입하며, 및 바인더와 담체를 10 중량% ~ 50 중량% 로 주입한 후 교반기 또는 혼합기로 혼합 반죽하여 압출기로 성형 제조한다.The composition ratio of the adsorbent for removing the acid exhaust gas according to the present invention is such that 10% by weight to 80% by weight of the transition metal is injected, 10% to 30% by weight of the ammonia composition is injected, By weight to 50% by weight, and the mixture is kneaded with a stirrer or a mixer and molded into an extruder.
보다 구체적으로, 본 발명은 탄산암모늄의 중량을 4% ~ 23%(중량%) 으로 하고 수산화알루미늄의 중량을 3% ~ 9% 으로 혼합하여 성형 제조된 산 배기가스 흡착제를 제공하는데 있다. More specifically, the present invention is to provide an acid exhaust gas adsorbent formed by mixing 4 to 23% (by weight) of ammonium carbonate and 3 to 9% by weight of aluminum hydroxide.
본 발명에 따른 산 배기가스 제거를 위한 흡착제의 착염물의 형태는 Ni(NH3)4(OH)2, Cu(NH3)4(OH)2, Zn(NH3)4(OH)2 를 갖는다.A complex salt form of water of the adsorbent for the acid exhaust gas removal according to the present invention has a Ni (NH 3) 4 (OH ) 2, Cu (NH 3) 4 (OH) 2, Zn (NH 3) 4 (OH) 2 .
피스톤 압출 성형기로 1.0 ~ 5.0 mm 크기로 압출 성형된 흡착제는 별도로 설계된 반응기에 25 ml 볼륨으로 제작하여 흡착제를 충진한 후 Cl2 가스(5000 ppm, N2 balance 표준가스)를 1 LPM 흘려주어 시간에 따른 Cl2 가스 흡착하여 제거하는 성능을 테스트하였다.The adsorbent extruded in 1.0 ~ 5.0 mm size by piston extrusion molding machine was prepared with a volume of 25 ml in a specially designed reactor, filled with adsorbent, and flowed with 1 LPM of Cl 2 gas (5000 ppm, N 2 balance standard gas) And the adsorbed Cl 2 gas was removed.
본 발명에 따라 제조된 흡착제의 상승된 효과를 살펴보기 위하여 아래와 같은 실험을 하였다.The following experiments were conducted to investigate the enhanced effect of the adsorbent prepared according to the present invention.
Cl2 가스의 유량은 볼 플로우메터(ball flowmeter)로 제어하였으며 반응기의 상단에 pH 검지지를 위치시켜 pH 검지지의 색깔이 산(acid)으로 변화되는 시점을 기준으로 하였다.The flow rate of the Cl 2 gas was controlled by a ball flow meter and the pH probe paper was placed on the top of the reactor to refer to the point where the color of the pH probe paper changed into acid.
<실시 예1> ≪ Example 1 >
구리 하이드로옥사이드(Copper hydroxide)를 이용하여 본 발명에 따라 제조된 흡착제를 테스트 하였다. 이때 원료의 중량은 구리 하이드로옥사이드(Copper hydroxide) 300 g, 요소 150 g, 탄산암모늄 25 g, 수산화알루미늄 25 g 그리고 규조토 100 g 이다.The adsorbent prepared according to the present invention was tested using copper hydroxide. The weight of the raw material is 300 g of copper hydroxide, 150 g of urea, 25 g of ammonium carbonate, 25 g of aluminum hydroxide and 100 g of diatomaceous earth.
90분 건조시킨 반응 흡착제의 경우에 산 배기가스 처리량은 30.4 L/L이고, 300분 건조시킨 반응 흡착제의 경우에 처리량은 22.4 L/L 이다.The acid exhaust gas throughput was 30.4 L / L for a reaction adsorbent dried for 90 minutes and the throughput was 22.4 L / L for a reaction sorbent dried for 300 minutes.
여기서 300분을 건조시킨 반응 흡착제의 경우 완전한 건조가 이루어진 상태를 의미한다. Here, in the case of the reaction adsorbent dried for 300 minutes, it means that the complete drying is performed.
30.4 L/L의 의미는 촉매 1리터 당 Cl2 가스(5000 ppm, N2 balance 표준가스) 30.4 리터를 100% 처리할 수 있음을 의미하며, 22.4 L/L의 의미는 촉매 1리터 당 Cl2 가스(5000 ppm, N2 balance 표준가스) 22.4 리터를 100% 처리(완전히 제거)할 수 있음을 의미한다.30.4 L / L means that 30.4 liters of Cl 2 gas (5000 ppm, N 2 balance standard gas) per 100 liters of catalyst can be treated 100%, and 22.4 L / L means that Cl 2 It means that 22.4 liters of gas (5000 ppm, N 2 balance standard gas) can be treated 100% (completely removed).
<실시 예2>≪ Example 2 >
실시 예1에서 구리 하이드로옥사이드(Copper hydroxide) 대신에 니켈 하이드로옥사이드(Nickel hydroxide)를 이용하여 본 발명에 따라 제조된 흡착제의 성능을 테스트 하였다.In Example 1, the performance of the adsorbent prepared according to the present invention was tested using nickel hydroxides instead of copper hydroxide.
90분 건조시킨 흡착제의 경우에 산 배기가스 처리량은 32.0 L/L 이고, 300분 건조시킨 흡착제의 경우에 흡착제의 산 배기가스 처리량은 20.0 L/L 이다.The acid exhaust gas throughput of the adsorbent dried for 90 minutes is 32.0 L / L and the adsorbent acid exhaust gas throughput of the adsorbent dried for 300 minutes is 20.0 L / L.
<실시 예3> ≪ Example 3 >
실시 예1에서 구리 하이드로옥사이드(Copper hydroxide) 대신에 아연 하이드로옥사이드(Zinc hydroxide)를 이용하여 본 발명에 따라 제조된 흡착제의 성능을 테스트 하였다.In Example 1, the performance of the adsorbent prepared according to the present invention was tested using zinc hydroxide instead of copper hydroxide.
90분 건조시킨 흡착제의 경우에 산 배기가스 처리량은 39.0 L/L 이고, 300분 건조시킨 약제의 경우에 처리량은 29.4 L/L 이다.The acid exhaust gas throughput was 39.0 L / L for a 90 minute dry adsorbent and 29.4 L / L for a 300 minute dry.
본 발명은 산 배기가스 (AlCl3, BCl3, HCl, HF, Cl2, HBr, BF3)를 효율적으로 처리할 수 있는 흡착제에 관한 것이며 보다 구체적으로 산 배기가스를 처리하기 위하여 Ni/Cu 수산화물 또는 Zinc 수산화물, 탄산암모늄, 규조토 그리고 수산화알루미늄의 최적량을 조사 하여 이를 바탕으로 산 배기가스 제거 성능 테스트 결과 Cl2 흡착량 최대 39.0L/L를 가짐을 확인하였다.The present invention relates to an adsorbent capable of effectively treating acid exhaust gas (AlCl 3 , BCl 3 , HCl, HF, Cl 2 , HBr, BF 3 ) Or Zinc hydroxide, ammonium carbonate, diatomaceous earth and aluminum hydroxide, and it was confirmed that the adsorption amount of Cl 2 was maximum 39.0 L / L as a result of acid exhaust gas removal performance test.
국내 기업의 반도체 제조 라인 에칭(etching) 공정에서 발생하는 산 배기가스를 제거하고자 자체 제작한 건조 스크러버 캔니스터(dry scrubber canister)에 상기에서 개발한 CT-150을 충진하고 현장에 적용 시험을 준비 중에 있으며 향후 국내 기업 납품을 예정하고 있어 산업상 이용 가능성이 매우 높다. In order to remove the acid exhaust gas generated in the semiconductor manufacturing line etching process of a domestic company, a self-made dry scrubber canister is filled with the CT-150 developed above, The company plans to supply domestic companies in the future, so it is very likely to be used in the industry.
Claims (6)
염소(Cl2) 가스 제거용 흡착제에서 전이금속은 Cu, Ni, Zn, Co 중에서 하나 이상을 선택하여 중량비 5 % ~ 60% 의 조성비로 하고,
암모니아수 (NH4OH), 탄산암모늄 ((NH4)2CO3), 요소 ((NH2)2CO) 및 중탄산암모늄 (NH4HCO3) 중에서 하나 이상을 선택하여 중량비 5 % ~ 60 % 의 조성비로 하며,
담체와 바인더의 중량비 10 % ~ 50 % 로 혼합 교반하여 압출 성형한 후 건조시켜 제조함을 특징으로 하는 염소(Cl2) 가스 제거용 흡착제.In the adsorbent for removing chlorine (Cl 2 ) gas,
In the adsorbent for removing chlorine (Cl 2 ) gas, at least one of Cu, Ni, Zn, and Co is selected as a transition metal and a composition ratio of 5% to 60%
At least one of ammonia water (NH 4 OH), ammonium carbonate ((NH 4 ) 2 CO 3 ), urea ((NH 2 ) 2 CO) and ammonium bicarbonate (NH 4 HCO 3 ) Composition ratio,
And the mixture is mixed and stirred at a weight ratio of the carrier and the binder of 10% to 50%, followed by extrusion molding, followed by drying, to obtain an adsorbent for removing chlorine (Cl 2 ) gas.
담체와 바인더는 규소 산화물, 규소 수산화물, 천연제올라이트, 활성알루미나, 수산화알루미늄 및 규조토 중에서 하나 이상을 선택하여 혼합 제조된 염소(Cl2) 가스 제거용 흡착제.The method according to claim 1,
The adsorbent for removing chlorine (Cl 2 ) gas produced by mixing at least one selected from the group consisting of silicon oxide, silicon hydroxide, natural zeolite, activated alumina, aluminum hydroxide and diatomaceous earth.
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