KR102496171B1 - Purification method for cos with removal of hydrogen sulfide - Google Patents
Purification method for cos with removal of hydrogen sulfide Download PDFInfo
- Publication number
- KR102496171B1 KR102496171B1 KR1020200176087A KR20200176087A KR102496171B1 KR 102496171 B1 KR102496171 B1 KR 102496171B1 KR 1020200176087 A KR1020200176087 A KR 1020200176087A KR 20200176087 A KR20200176087 A KR 20200176087A KR 102496171 B1 KR102496171 B1 KR 102496171B1
- Authority
- KR
- South Korea
- Prior art keywords
- hydrogen sulfide
- sulfide
- gas
- carbonyl sulfide
- cos
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/70—Compounds containing carbon and sulfur, e.g. thiophosgene
- C01B32/77—Carbon oxysulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/261—Drying gases or vapours by adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/263—Drying gases or vapours by absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0003—Chemical processing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/0014—Physical processing by adsorption in solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0062—Water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0064—Hydrogen sulfide
Abstract
본 발명은 황화수소(H2S)를 불순물로 포함하는 조질의 황화카르보닐(COS) 가스를 정제하는 방법에 관한 것으로, 보다 상세하게는 메틸디에탄올아민(MDEA) 및 탄산나트륨(Na2CO3) 중 적어도 하나를 포함하는 수용액과 접촉시켜 황화수소를 제거하는 단계를 포함하는 황화카르보닐 가스를 정제하는 방법에 관한 것이다. 본 발명에 의하면, 황화수소를 불순물로 포함하는 조질의 황화카르보닐 가스로부터 황화수소를 제거함으로써 순도가 99% 이상인 고순도의 황화카르보닐 가스를 수득할 수 있어 상기 황화카르보닐 가스의 정제를 위해 증류 공정에서 소비되는 에너지를 저감할 수 있고 증류탑의 크기를 감소시킬 수 있다.The present invention relates to a method for purifying crude carbonyl sulfide (COS) gas containing hydrogen sulfide (H 2 S) as an impurity, and more particularly, to methyldiethanolamine (MDEA) and sodium carbonate (Na 2 CO 3 ) It relates to a method for purifying carbonyl sulfide gas comprising the step of contacting an aqueous solution containing at least one of the following to remove hydrogen sulfide. According to the present invention, by removing hydrogen sulfide from the crude carbonyl sulfide gas containing hydrogen sulfide as an impurity, it is possible to obtain a high-purity carbonyl sulfide gas having a purity of 99% or more. Energy consumed can be reduced and the size of the distillation column can be reduced.
Description
본 발명은 황화수소(H2S)를 불순물로 포함하는 조질의 황화카르보닐(COS) 가스를 정제하는 방법에 관한 것으로, 보다 상세하게는 메틸디에탄올아민(MDEA) 및 탄산나트륨(Na2CO3) 중 적어도 하나를 포함하는 수용액과 접촉시켜 황화수소를 제거하는 단계를 포함하는 황화카르보닐 가스를 정제하는 방법에 관한 것이다.The present invention relates to a method for purifying crude carbonyl sulfide (COS) gas containing hydrogen sulfide (H 2 S) as an impurity, and more particularly, to methyldiethanolamine (MDEA) and sodium carbonate (Na 2 CO 3 ) It relates to a method for purifying carbonyl sulfide gas comprising the step of contacting an aqueous solution containing at least one of the following to remove hydrogen sulfide.
황화카르보닐(Carbonyl sulfide, COS) 가스는 무색의 가연성 가스로 반도체 공정에서 에칭 가스(Etching gas)로 사용된다. 에칭이란 반도체 웨이퍼에 불필요한 부분을 화학물질이나 특수가스를 사용해 제거하는 공정을 의미하며 건식 에칭, 플라즈마 에칭 등이 있다. 상기 에칭 가스로서 황화카르보닐의 사용이 점차 늘어나는 추세이다.Carbonyl sulfide (COS) gas is a colorless, flammable gas used as an etching gas in a semiconductor process. Etching refers to a process of removing unnecessary parts of a semiconductor wafer using chemicals or special gases, and includes dry etching and plasma etching. The use of carbonyl sulfide as the etching gas is gradually increasing.
황화카르보닐 가스를 합성하여 제조하는 경우, 합성된 황화카르보닐가스는 필연적으로 공급원 또는 제조과정으로부터 발생한 황화수소(H2S), 이산화탄소(CO2) 및 이황화탄소(CS2)와 같은 불순물을 포함한다.When synthesizing and producing carbonyl sulfide gas, the synthesized carbonyl sulfide gas inevitably contains impurities such as hydrogen sulfide (H 2 S), carbon dioxide (CO 2 ) and carbon disulfide (CS 2 ) generated from sources or manufacturing processes. do.
황화카르보닐 가스의 주요 불순물에 해당하는 황화수소는 극소량만이 존재하는 경우에도 구리의 부식을 촉진하는 특성을 가지므로 반도체 공정에 치명적인 영향을 끼친다. 또한, 물(H2O) 존재 시 황화카르보닐 가스와 물이 반응하여 황화수소가 생성될 수 있다. 따라서 불순물이 제거된 고순도의 황화카르보닐 가스가 요구된다.Hydrogen sulfide, which is a major impurity of carbonyl sulfide gas, has a property of accelerating copper corrosion even when it is present in a very small amount, and thus has a fatal effect on semiconductor processes. In addition, in the presence of water (H 2 O), carbonyl sulfide gas and water may react to generate hydrogen sulfide. Therefore, high-purity carbonyl sulfide gas from which impurities are removed is required.
기존의 황화카르보닐 정제 방법은 흡착 공정 및 증류 공정을 포함하나, 미정제된 황화카르보닐(Crude COS) 가스로부터 황화수소를 제거하는 효율이 낮은 문제가 있다. 증류 공정에서 황화카르보닐과 황화수소의 비점(Boiling point) 차이가 크지 않아 비슷한 휘발성을 갖기 때문에 황화카르보닐 가스를 정제하기 위해 과도한 증류 에너지가 소모되고, 증류탑의 크기가 커져 초기 투자 비용이 과도하게 소요되므로 비경제적이다.Existing carbonyl sulfide purification methods include an adsorption process and a distillation process, but there is a problem in that the efficiency of removing hydrogen sulfide from crude carbonyl sulfide (Crude COS) gas is low. In the distillation process, the difference in boiling point between carbonyl sulfide and hydrogen sulfide is not large, so they have similar volatility, so excessive distillation energy is consumed to purify carbonyl sulfide gas, and the size of the distillation column increases, so the initial investment cost is excessive. so it is uneconomical.
한편, 한국 공개특허10-2012-0008534호에는 아연을 포함하는 흡착제를 이용하여 불순물을 포함하는 황화카르보닐 가스에서 황화수소(H2S)를 제거하는 방법이 기재되어 있다.Meanwhile, Korean Patent Publication No. 10-2012-0008534 discloses a method of removing hydrogen sulfide (H 2 S) from carbonyl sulfide gas containing impurities using an adsorbent containing zinc.
이에, 비교적 간편한 공정으로 COS를 포함하는 가스에서 황화수소(H2S)를 선택적으로 제거하는 방법이 제공되는 경우 관련 분야에서 유용하게 사용될 수 있을 것으로 기대된다.Accordingly, when a method for selectively removing hydrogen sulfide (H 2 S) from a gas containing COS with a relatively simple process is provided, it is expected to be useful in related fields.
본 발명은 메틸디에탄올아민 및 탄산나트륨 중 적어도 하나를 포함하는 수용액을 이용하여 황화수소를 불순물로 포함하는 조질의 황화카르보닐 가스로부터 황화수소를 제거하는 방법을 제공하는 것이다.The present invention is methyldiethanolamine and sodium carbonate It is to provide a method for removing hydrogen sulfide from a crude carbonyl sulfide gas containing hydrogen sulfide as an impurity by using an aqueous solution containing at least one of the above.
본 발명의 일 견지에 의하면, 황화수소를 불순물로 포함하는 조질의 황화카르보닐 가스를 메틸디에탄올아민 및 탄산나트륨 중 적어도 하나를 포함하는 수용액과 접촉시켜 황화수소를 제거하는 단계를 포함하는, 황화카르보닐 가스를 정제하는 방법이 제공된다.According to one aspect of the present invention, crude carbonyl sulfide gas containing hydrogen sulfide as an impurity is mixed with methyldiethanolamine and sodium carbonate There is provided a method for purifying carbonyl sulfide gas, comprising the step of removing hydrogen sulfide by contacting it with an aqueous solution containing at least one of.
본 발명에 의하면, 황화수소를 불순물로 포함하는 조질의 황화카르보닐 가스로부터 황화수소를 제거함으로써 순도가 99% 이상인 고순도의 황화카르보닐 가스를 수득할 수 있어 상기 황화카르보닐 가스의 정제를 위해 증류 공정에서 소비되는 에너지를 저감할 수 있고 증류탑의 크기를 감소시킬 수 있다.According to the present invention, by removing hydrogen sulfide from the crude carbonyl sulfide gas containing hydrogen sulfide as an impurity, it is possible to obtain a high-purity carbonyl sulfide gas having a purity of 99% or more. Energy consumed can be reduced and the size of the distillation column can be reduced.
도 1은 본 발명의 황화카르보닐 가스를 정제하는 방법의 간략한 모식도를 나타낸 것이다.1 shows a simplified schematic diagram of a method for purifying carbonyl sulfide gas according to the present invention.
이하, 본 발명의 바람직한 실시 형태를 설명한다. 그러나, 본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention may be modified in various forms, and the scope of the present invention is not limited to the embodiments described below.
본 발명은 황화수소(H2S)를 불순물로 포함하는 조질의 황화카르보닐(Carbonyl sulfide, COS) 가스를 처리 대상으로 하며, 상기 가스로부터 황화수소를 제거하여 황화카르보닐 가스를 정제하는 방법에 관한 것이다.The present invention relates to a process for treating crude carbonyl sulfide (COS) gas containing hydrogen sulfide (H 2 S) as an impurity, and to a method for purifying carbonyl sulfide gas by removing hydrogen sulfide from the gas .
보다 상세하게, 황화수소를 불순물로 포함하는 조질의 황화카르보닐 가스를 메틸디에탄올아민(MDEA) 및 탄산나트륨(Na2CO3) 중 적어도 하나를 포함하는 수용액과 접촉시켜 황화수소를 제거하는 단계를 포함하는, 황화카르보닐 가스를 정제하는 방법에 관한 것이다.More specifically, crude carbonyl sulfide gas containing hydrogen sulfide as an impurity is mixed with methyldiethanolamine (MDEA) and sodium carbonate (Na 2 CO 3 ). It relates to a method for purifying carbonyl sulfide gas, comprising the step of contacting an aqueous solution containing at least one of the following to remove hydrogen sulfide.
상기 황화카르보닐 가스에 불순물로 포함된 황화수소(H2S)의 농도는 20 내지 25,000ppm일 수 있다.The concentration of hydrogen sulfide (H 2 S) included as an impurity in the carbonyl sulfide gas may be 20 to 25,000 ppm.
나아가, 상기 황화수소를 불순물로 포함하는 조질의 황화카르보닐 가스는 황화수소(H2S) 외에도 불순물로 물(H2O), 이산화탄소(CO2), 일산화탄소(CO), 이황화탄소(CS2), 메탄(CH4), 질소(N2), 산소(O2), 수소(H2)로 이루어지는 그룹으로부터 선택되는 하나 이상을 추가로 포함할 수 있으나, 이에 제한되는 것은 아니며, 황화카르보닐 가스에 포함된 불순물의 전체 농도는 100 내지 100,000ppm일 수 있다.Furthermore, the crude carbonyl sulfide gas containing hydrogen sulfide as an impurity contains water (H 2 O), carbon dioxide (CO 2 ), carbon monoxide (CO), carbon disulfide (CS 2 ) as impurities in addition to hydrogen sulfide (H 2 S), It may further include one or more selected from the group consisting of methane (CH 4 ), nitrogen (N 2 ), oxygen (O 2 ), and hydrogen (H 2 ), but is not limited thereto. The total concentration of included impurities may be 100 to 100,000 ppm.
이에 따라, 상기 황화수소를 불순물로 포함하는 조질의 황화카르보닐 가스는 증류 공정 또는 흡착 공정 중 적어도 하나를 수행하여 일차적으로 불순물을 제거한 것일 수 있으나, 이에 특히 제한되는 것은 아니며, 불순물로 포함된 황화수소의 농도가 20 내지 25,000ppm인 황화카르보닐 가스라면 제한 없이 사용할 수 있다.Accordingly, the crude carbonyl sulfide gas containing hydrogen sulfide as an impurity may be obtained by first removing impurities by performing at least one of a distillation process and an adsorption process, but is not particularly limited thereto. Any carbonyl sulfide gas having a concentration of 20 to 25,000 ppm may be used without limitation.
본 발명에 있어서, 황화수소를 불순물로 포함하는 조질의 황화카르보닐 가스를 메틸디에탄올아민 및 탄산나트륨 중 적어도 하나를 포함하는 수용액과 접촉시켜 황화수소를 제거하는 단계는, 특별히 한정하지 않으나, 예를 들어 황화수소를 불순물로 포함하는 조질의 황화카르보닐 가스를 메틸디에탄올아민 및 탄산나트륨 중 적어도 하나를 포함하는 수용액이 담긴 저장용기 내부로 주입하여 버블링(bubbling)하거나, 탑(tower)의 하부에 상기 가스를 주입하고 탑(tower)의 상부에서 상기 수용액을 분무하는 방식 등으로 접촉시킬 수 있다. 예를 들어, 충진탑(packed tower) 또는 다단탑(tray tower)의 하부에 상기 가스를 공급하고 상기 탑의 상부에서 수용액을 분무하는 방식으로 접촉시키는 경우 기체-액체 간 접촉 면적이 증가하여 황화수소의 제거 효율이 증가할 수 있다.In the present invention, the step of removing hydrogen sulfide by contacting crude carbonyl sulfide gas containing hydrogen sulfide as an impurity with an aqueous solution containing at least one of methyldiethanolamine and sodium carbonate is not particularly limited, but, for example, hydrogen sulfide Crude carbonyl sulfide gas containing as an impurity is converted to methyldiethanolamine and sodium carbonate Injecting and bubbling into a storage container containing an aqueous solution containing at least one of the above, or injecting the gas into the lower part of a tower and spraying the aqueous solution from the upper part of the tower, etc. can make it For example, when the gas is supplied to the lower part of a packed tower or a tray tower and the aqueous solution is sprayed from the upper part of the tower, the gas-liquid contact area increases, so that hydrogen sulfide Removal efficiency may be increased.
상기 메틸디에탄올아민 및 탄산나트륨 중 적어도 하나를 포함하는 수용액은, 메틸디에탄올아민 수용액, 탄산나트륨 수용액, 또는 메틸디에탄올아민 및 탄산나트륨의 혼합 수용액일 수 있다.The aqueous solution containing at least one of methyldiethanolamine and sodium carbonate may be an aqueous solution of methyldiethanolamine, an aqueous solution of sodium carbonate, or a mixed aqueous solution of methyldiethanolamine and sodium carbonate.
상기 수용액이 메틸디에탄올아민을 포함하는 경우, 상기 메틸디에탄올아민은 전체 수용액 중량을 기준으로 10 내지 60중량% 포함되는 것이 바람직하고, 30 내지 50중량% 포함되는 것이 보다 바람직하다. 10중량% 미만의 경우, 에너지 효율이 좋지 않고, 60중량% 초과의 경우, 액체의 점도와 부식성이 과도하게 높은 문제가 있다.When the aqueous solution contains methyldiethanolamine, the methyldiethanolamine is preferably included in an amount of 10 to 60% by weight, more preferably 30 to 50% by weight based on the total weight of the aqueous solution. In the case of less than 10% by weight, energy efficiency is not good, and in the case of more than 60% by weight, there is a problem that the viscosity and corrosiveness of the liquid are excessively high.
상기 수용액이 탄산나트륨을 포함하는 경우, 상기 탄산나트륨은 전체 수용액 중량을 기준으로 10 내지 30중량% 포함되는 것이 바람직하고, 15 내지 25중량% 포함되는 것이 보다 바람직하다. 10중량% 미만의 경우 에너지 효율이 좋지 않은 문제가 있고, 30중량% 초과의 경우, 탄산나트륨이 석출되는 문제가 있다.When the aqueous solution contains sodium carbonate, the sodium carbonate is preferably included in an amount of 10 to 30% by weight, and 15 to 25% by weight based on the total weight of the aqueous solution. more preferable In the case of less than 10% by weight, there is a problem of poor energy efficiency, and in the case of more than 30% by weight, there is a problem in that sodium carbonate is precipitated.
한편, 상기 메틸디에탄올아민 및 탄산나트륨을 사용하여 황화수소를 불순물로 포함하는 조질의 황화 카르보닐 가스에서 황화수소를 선택적으로 제거할 수 있다.On the other hand, using the methyldiethanolamine and sodium carbonate Hydrogen sulfide can be selectively removed from crude carbonyl sulfide gas containing hydrogen sulfide as an impurity.
본 발명에 있어서, 선택적으로 제거한다는 것은 황화수소를 불순물로 포함하는 조질의 황화카르보닐 가스로부터 황화수소를 황화카르보닐과 동시에 제거하는 것이 아닌, 황화카르보닐이 제거되는 것을 방지하면서 황화수소를 선택적으로 제거하는 것을 의미한다.In the present invention, selectively removing hydrogen sulfide is not to remove hydrogen sulfide from the crude carbonyl sulfide gas containing hydrogen sulfide as an impurity at the same time as carbonyl sulfide, but to selectively remove hydrogen sulfide while preventing carbonyl sulfide from being removed. means that
상기 메틸디에탄올아민이 황화수소와 접촉하는 경우 하기와 같은 반응이 수반될 수 있다.When the methyldiethanolamine is brought into contact with hydrogen sulfide, the following reaction may be accompanied.
MDEA + H2S → MDEAH+ + HS- MDEA + H 2 S → MDEAH + + HS -
상기 반응은 0.01 내지 5초 이내에 이루어질 수 있다. 그러나, 메틸디에탄올아민이 황화카르보닐과 접촉하는 경우에는 황화카르보닐과 직접 반응하지 못하고, 황화카르보닐이 가수분해되어 생성된 황화수소와 반응할 수 있다. 상기 반응은 하기와 같다.The reaction can be made within 0.01 to 5 seconds. However, when methyldiethanolamine comes into contact with carbonyl sulfide, it does not directly react with carbonyl sulfide, but may react with hydrogen sulfide generated by hydrolysis of carbonyl sulfide. The reaction is as follows.
COS + H2O → H2S + CO2 → HCO2S- + H+ COS + H 2 O → H 2 S + CO 2 → HCO 2 S - + H +
COS + H2O + MDEA → HCO2S- + MDEAH+ COS + H 2 O + MDEA → HCO 2 S - + MDEAH +
한편, 탄산나트륨은 황화수소와 접촉하는 경우 하기와 같은 반응을 수행할 수 있다.On the other hand, when sodium carbonate comes into contact with hydrogen sulfide, the following reaction may be performed.
H2S + Na2CO3 → NaHS + NaHCO3 H 2 S + Na 2 CO 3 → NaHS + NaHCO 3
상기 반응은 0.01 내지 5초 이내에 이루어질 수 있다. 그러나, 탄산나트륨이 황화카르보닐과 접촉하는 경우에는 황화카르보닐과 직접 반응하지 못하고, 황화카르보닐이 가수분해되어 생성된 황화수소와 반응할 수 있다. 상기 반응은 하기와 같다.The reaction can be made within 0.01 to 5 seconds. However, when sodium carbonate comes into contact with carbonyl sulfide, it does not directly react with carbonyl sulfide, but may react with hydrogen sulfide generated by hydrolysis of carbonyl sulfide. The reaction is as follows.
COS + H2O → H2S + CO2 COS + H 2 O → H 2 S + CO 2
COS + H2O + Na2CO3 → NaHS + NaHCO3 + CO2 COS + H 2 O + Na 2 CO 3 → NaHS + NaHCO 3 + CO 2
즉, 황화수소의 선택적 제거를 위해서는 황화카르보닐이 가수분해되기 전에 황화수소를 제거하는 단계를 종료해야 한다. 따라서, 상기 황화수소(H2S)를 제거하는 단계는 0.01내지 5초간 수행될 수 있고, 0.1내지 3초간 수행되는 것이 보다 바람직하다. 0.01초 미만인 경우, 황화수소가 수용액 내의 메틸디에탄올아민 또는 탄산나트륨과 충분히 반응하지 못하는 문제가 있고, 5초 초과인 경우, 황화카르보닐이 수용액 내에서 가수분해 되어 황화수소가 다시 생성되므로 황화수소의 제거 효율이 떨어진다.That is, in order to selectively remove hydrogen sulfide, the step of removing hydrogen sulfide must be completed before carbonyl sulfide is hydrolyzed. Therefore, the step of removing the hydrogen sulfide (H 2 S) may be performed for 0.01 to 5 seconds, and more preferably performed for 0.1 to 3 seconds. If it is less than 0.01 seconds, there is a problem that hydrogen sulfide does not sufficiently react with methyldiethanolamine or sodium carbonate in the aqueous solution, and if it exceeds 5 seconds, carbonyl sulfide is hydrolyzed in the aqueous solution to generate hydrogen sulfide again, so the removal efficiency of hydrogen sulfide increases. It falls.
한편, 본 발명의 황화카르보닐 가스를 정제하는 방법은 수분을 제거하는 단계를 추가로 포함할 수 있으며, 예를 들어 활성탄, 실리카겔, 제올라이트와 같은 수분 흡착제 또는 TEG(triethylene glycol)과 같은 수분 흡수제를 이용하여 수분을 제거할 수 있고, 바람직하게는 수분 흡착제를 이용하여 수분을 제거할 수 있다.On the other hand, the method of purifying carbonyl sulfide gas of the present invention may further include a step of removing moisture, for example, using a moisture adsorbent such as activated carbon, silica gel, or zeolite or a moisture absorbent such as triethylene glycol (TEG). Moisture can be removed by using, preferably, moisture can be removed by using a moisture adsorbent.
상기 수분을 제거하는 단계가 황화수소를 제거하는 단계 이후에 수행되는 경우, 황화카르보닐이 가수분해 되어 황화수소가 생성되는 것을 방지할 수 있다.When the step of removing moisture is performed after the step of removing hydrogen sulfide, it is possible to prevent carbonyl sulfide from being hydrolyzed to produce hydrogen sulfide.
나아가, 본 발명의 황화수소를 정제하는 방법을 수행하여 순도가 99% 이상인 고순도의 황화카르보닐 가스를 수득할 수 있다.Furthermore, by carrying out the method of purifying hydrogen sulfide of the present invention, a high-purity carbonyl sulfide gas having a purity of 99% or more can be obtained.
이하, 구체적인 실시예를 통해 본 발명을 보다 구체적으로 설명한다. 하기 실시예는 본 발명의 이해를 돕기 위한 예시에 불과하며, 본 발명의 범위가 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.
실시예Example
실시예 1Example 1
표준상태에서, 하기 표 1과 같은 조성을 가지는 가스를 준비하였다.In a standard state, a gas having the composition shown in Table 1 below was prepared.
ppm5,173
ppm
ppm<10
ppm
ppm538
ppm
ppm144
ppm
ppm1,390
ppm
ppm99.2
ppm
ppm10.9
ppm
상온(25℃)에서 상기 가스를 메틸디에탄올아민 1L 및 물 1L를 혼합한 수용액 2L가 담긴 저장용기 내부로 주입하여 3초간 버블링(bubbling)을 수행하였다.At room temperature (25° C.), the gas was injected into a storage container containing 2 L of an aqueous solution obtained by mixing 1 L of methyldiethanolamine and 1 L of water, and bubbling was performed for 3 seconds.
접촉 후 회수된 가스에 포함된 황화수소의 농도를 검지관(가스테크사 제조)을 이용하여 측정하였다.The concentration of hydrogen sulfide contained in the recovered gas after contact was measured using a detector tube (manufactured by Gastech).
회수된 가스의 황화수소 농도는 20ppm로 측정되었다.The hydrogen sulfide concentration of the recovered gas was measured to be 20 ppm.
실시예 2Example 2
메틸디에탄올아민 수용액 대신, 탄산나트륨 분말 200g을 물 1L에 용해한 탄산나트륨 수용액을 사용한 것을 제외하고, 실시예 1과 동일한 방법을 수행하여 회수한 가스에 포함된 황화수소의 농도를 측정하였다.The concentration of hydrogen sulfide contained in the recovered gas was measured in the same manner as in Example 1, except that an aqueous sodium carbonate solution obtained by dissolving 200 g of sodium carbonate powder in 1 L of water was used instead of the aqueous solution of methyldiethanolamine.
회수한 가스의 황화수소 농도는 10ppm로 측정되었다.The concentration of hydrogen sulfide in the recovered gas was measured to be 10 ppm.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and variations are possible without departing from the technical spirit of the present invention described in the claims. It will be obvious to those skilled in the art.
Claims (7)
수분 흡착제 또는 수분 흡수제를 이용하여 수분을 제거하는 단계를 포함하며,
상기 조질의 황화카르보닐(COS) 가스는 순도가 90% 이상이고,
상기 황화수소(H2S)를 제거하는 단계는 조질의 황화카르보닐(COS) 가스를 상기 수용액과 0.01 내지 5초간 접촉시켜 수행되는, 황화카르보닐 가스를 정제하는 방법.
Removing hydrogen sulfide (H 2 S) by contacting a crude carbonyl sulfide (COS) gas containing hydrogen sulfide (H 2 S) as an impurity with an aqueous solution containing 10 to 30% by weight of sodium carbonate (Na 2 CO 3 ) ; and
Including the step of removing moisture using a moisture absorbent or moisture absorbent,
The crude carbonyl sulfide (COS) gas has a purity of 90% or more,
The step of removing the hydrogen sulfide (H 2 S) is performed by contacting the crude carbonyl sulfide (COS) gas with the aqueous solution for 0.01 to 5 seconds, a method for purifying carbonyl sulfide gas.
The method of claim 1, wherein the crude carbonyl sulfide gas contains 20 to 25,000 ppm of hydrogen sulfide (H 2 S).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020200176087A KR102496171B1 (en) | 2020-12-16 | 2020-12-16 | Purification method for cos with removal of hydrogen sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020200176087A KR102496171B1 (en) | 2020-12-16 | 2020-12-16 | Purification method for cos with removal of hydrogen sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20220086011A KR20220086011A (en) | 2022-06-23 |
| KR102496171B1 true KR102496171B1 (en) | 2023-02-06 |
Family
ID=82222056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020200176087A KR102496171B1 (en) | 2020-12-16 | 2020-12-16 | Purification method for cos with removal of hydrogen sulfide |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102496171B1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013212950A (en) * | 2012-04-02 | 2013-10-17 | Toagosei Co Ltd | Method for producing high purity carbonyl sulfide |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0322924A1 (en) * | 1987-12-31 | 1989-07-05 | Union Carbide Corporation | Selective H2S removal from fluid mixtures using high purity triethanolamine |
| JPH0722670B2 (en) * | 1989-06-12 | 1995-03-15 | 川崎製鉄株式会社 | Method for dry removal of organic sulfur compounds in gas |
| KR100450224B1 (en) * | 2000-08-24 | 2004-09-24 | 주식회사 포스코 | Method for removing hydrogen sulfide of coke oven gas |
| JP2012522089A (en) * | 2009-03-30 | 2012-09-20 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Method for generating a purified syngas stream |
| KR20130059755A (en) * | 2011-11-29 | 2013-06-07 | 재단법인 포항산업과학연구원 | Method for removing hydrogen sulfate from blast furnace slag by using sodium carbornate |
| KR20200000644A (en) * | 2018-06-25 | 2020-01-03 | 포항공과대학교 산학협력단 | Solution for removing hydrogen sulfide in gas, apparatus for removing hydrogen sulfide in gas |
-
2020
- 2020-12-16 KR KR1020200176087A patent/KR102496171B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013212950A (en) * | 2012-04-02 | 2013-10-17 | Toagosei Co Ltd | Method for producing high purity carbonyl sulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20220086011A (en) | 2022-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100831093B1 (en) | Method for the separation and recycle of pure sulfur dioxide from gaseous mixture in the is cycle with ionic liquids | |
| CA1089842A (en) | Process and amine-solvent absorbent for removing acidic gases from gaseous mixtures | |
| RU2227060C2 (en) | Method of removal of the acidic nature gaseous ingredients from gases | |
| US4080424A (en) | Process for acid gas removal from gaseous mixtures | |
| US4044100A (en) | Separation of acidic gas constituents from gaseous mixtures containing the same | |
| EP2409752B1 (en) | Method for removing sox from gas using polyethylene glycol | |
| EP3059004A1 (en) | Method for removing sox from gas withncompound alcohol-amine solution | |
| US7387768B2 (en) | Method for purifying gases | |
| EP3081283A1 (en) | Method for removing sox in gas by using ethylene glycol complex solution | |
| US4556546A (en) | Bis tertiary amino alkyl derivatives as solvents for acid gas removal from gas streams | |
| CA1186490A (en) | Process for the removal of h.sub.2s and co.sub.2 from gaseous streams | |
| CA2637468A1 (en) | Process for purifying gaseous mixtures containing mercaptans and other acidic gases | |
| EP0344612A2 (en) | Process for purifying nitrogen trifluoride gas | |
| JP2016523691A (en) | Mixtures of physically absorbing solvents and ionic liquids for gas separation | |
| US3653810A (en) | Process for a fine purification of hydrogen-containing gases | |
| US4430312A (en) | Removal of CO2 from gas mixtures | |
| US3516793A (en) | Process for purifying sulfide containing gases and the recovery of sulfur therefrom | |
| KR101210929B1 (en) | Carbon dioxide absorbent and method of removal of carbon dioxide from landfill gas by the simultaneous generation of barium carbonate using the same | |
| KR102496171B1 (en) | Purification method for cos with removal of hydrogen sulfide | |
| CN101653688A (en) | Process flow for removing CO2 and H2S in gas mixture | |
| US4402930A (en) | Sulfur recovery process | |
| US4808341A (en) | Process for the separation of mercaptans contained in gas | |
| KR101223846B1 (en) | Method for removal of hydrogen sulfide by hydrogen sulfide removing agent | |
| CA1217036A (en) | Bis tertiary amino alkyl derivatives as solvents for acid gas removal from gas streams | |
| US3350165A (en) | Method of removing sulphur dioxide from gases |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |