KR890005042B1 - Reproducing method of wasted silicon oil - Google Patents

Reproducing method of wasted silicon oil Download PDF

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KR890005042B1
KR890005042B1 KR1019860010983A KR860010983A KR890005042B1 KR 890005042 B1 KR890005042 B1 KR 890005042B1 KR 1019860010983 A KR1019860010983 A KR 1019860010983A KR 860010983 A KR860010983 A KR 860010983A KR 890005042 B1 KR890005042 B1 KR 890005042B1
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hydrazine
silicon oil
oil
waste silicon
waste
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KR880007706A (en
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김병태
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
    • C10M175/0033—Working-up used lubricants to recover useful products ; Cleaning by thermal processes using distillation processes; devices therefor
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
    • C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes

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Abstract

A method for reproducing a waste silicon oil comprises (a) preparing a mixing gas (N2:H2=1:1) of a hydrazine by the pyrolysis of the hydrazine in the presence of palladium at 120≰C, (b) mixing the silicon oil with the mixing gas and deoxidizing, and (c) removing dust and impurities from the silicon oil by use of zeolite and active carbon.

Description

폐 실리콘유의 재생방법Recycling method of waste silicone oil

도면은 폐실리콘유의 재생공정도.The drawing shows the recycling process of waste silicon oil.

본 발명은 확산진공펌프에서 사용, 폐기되는 폐실리콘유를 파라듐(pd) 촉매존재하에서 제조된 히드라진의 분해 혼합가스에 의해 탈산시키고 제올라이트(Zeolite) 및 활성탄을 이용하여 불순물을 흡착 제거하는 폐실리콘유의 재생방법에 관한 것이다.The present invention is a waste silicon which deoxidized waste silicon oil used and used in a diffusion vacuum pump by decomposing mixed gas of hydrazine prepared in the presence of palladium (pd) catalyst and adsorbing and removing impurities using zeolite and activated carbon. The method relates to regeneration.

종래에는 TV브라운관 공장이나 원자력 발전소등의 진공장치에서 사용되고 폐기되는 폐실리콘유를 전량 폐기하였다.Conventionally, all of the used silicon oil used in a vacuum apparatus such as a TV brown tube plant or a nuclear power plant is disposed of.

그러나 실리콘유는 원래 고가이고 국내에서는 전량 수입에 의존하고 있는 실정이어서 이를 사용하고 폐기하면 물질적으로나 경제적으로 막대한 손실을 가져온다.However, since silicone oil is originally expensive and relies on imports in Korea, the use and disposal of it can cause enormous loss both materially and economically.

본 발명은 이와같은 물질적, 경제적인 손실을 감안하여 확산 진공펌프유로 사용되고 폐기되는 폐실리콘유를 파라듐 촉매 존재하에서 제조된 히드라진의 분해 혼합가스와 접촉시켜 탈산시키고 흡착제등을 이용하여 폐실리콘유를 재생시킴으로서 확산 진공펌프유로 사용되기 전의 실리콘과 동일한 순도의 재생 실리콘유를 제조하기에 이르렀다.In view of such material and economic losses, the present invention is to deoxidize waste silicon oil used and used as a diffusion vacuum pump oil by contacting with a decomposition mixed gas of hydrazine prepared in the presence of a palladium catalyst and using waste adsorbents to desorb the waste silicon oil. Regeneration has led to the production of regenerated silicone oil of the same purity as that used before the diffusion vacuum pump oil.

확산 진공펌프유로 사용되는 실리콘유는 다음과 같이 일반식 (Ⅰ)과 (Ⅱ)로 표시된다.Silicone oil used as the diffusion vacuum pump oil is represented by the general formulas (I) and (II) as follows.

Figure kpo00001
Figure kpo00001

상기 일반식 (Ⅱ)는 일반식 (Ⅰ)에서 Si에 부착되어 있는 메틸기중 하나가 페닐기로 치환된 화합물이며, 상기식중 n, x, y는 0 또는 1이상의 정수이고, x, y는 서로 같거나 다른 정수이다.General Formula (II) is a compound in which one of the methyl groups attached to Si in General Formula (I) is substituted with a phenyl group, wherein n, x, and y are integers of 0 or 1 or more, and x and y are mutually Equal to or different from integer.

본 발명에서 재생하고자 하는 폐실리콘은 상기 일반식 (Ⅰ),(Ⅱ)으로 표시되는 화합물을 진공펌프유로 진공상태에서 장시간 동안 사용하면 산소에 의해 산화되거나 또는 다른 물질등에 의해 오염되어 사용후 이를 폐기한다.The waste silicon to be recycled in the present invention is oxidized by oxygen or contaminated by other materials when used for a long time in a vacuum state using a compound represented by the general formulas (I) and (II) as a vacuum pump and then discarded after use. do.

본 발명에서 사용되는 확산진공 펌프의 진공압력은 보통 10-6Torr이기 때문에 완전한 진공상태라 할수 없다. 따라서 확산진공 펌프내에는 산소(O2), 질소(N2), 아르곤(Ar), CO2등의 대기가스가 극소량 함유되어 있어 진공과정시 산소에 의해 산화되며 기타 다른 물질에 의해 오염된다. 또한 확산 진공펌프를 설치하거나 보수를 할 경우에도 오염물이 부착된다.Since the vacuum pressure of the diffusion vacuum pump used in the present invention is usually 10 -6 Torr, it cannot be said that it is a complete vacuum. Therefore, the diffusion vacuum pump contains a very small amount of atmospheric gases such as oxygen (O 2 ), nitrogen (N 2 ), argon (Ar), CO 2 oxidized by oxygen during the vacuum process and are contaminated by other substances. In addition, contaminants are attached when installing or repairing a diffusion vacuum pump.

본 발명에서는 이러한 폐실리콘유를 재생하기 위해 파라듐 촉매 존재하에서 히드라진의 분해혼합가스와 흡착제등을 이용한다.In the present invention, a cracked mixed gas of hydrazine, an adsorbent, and the like are used in the presence of a palladium catalyst to regenerate the waste silicon oil.

탈산제로서는 수소(H2)가스를 사용하여야 하나 H2가스를 단독으로 사용할 경우 폭발등의 위험성이 있으므로 본 발명에서는 히드라진을 120-350℃에서 열분해 하여 얻어진 H2와 N2의 혼합가스를 사용한다.As the deoxidizer, hydrogen (H 2 ) gas should be used. However, when H 2 gas is used alone, there is a risk of explosion. In the present invention, a mixed gas of H 2 and N 2 obtained by pyrolyzing hydrazine at 120-350 ° C. is used. .

히드라진은 보통 액상의 수화 히드라진(N2H4·H2O)으로 저장되기 때문에 수화 히드라진에서 수분(H2O)를 제거한 후 순수한 히드라진을 사용한다. 수화 히드라진중 수분은 고압 보일러로 부터 공급되는 120℃의 스팀이 가열공급되고 가성소다(NaOH)가 충진된 히드라진 발생장치에 통과시켜 제거한다. 이 히드라진은 파라듐 촉매 존재하에서 열분해하면 다음과 같다.Since hydrazine is usually stored as a liquid hydrated hydrazine (N 2 H 4 · H 2 O), pure hydrazine is used after removing water (H 2 O) from the hydrated hydrazine. Water in the hydrated hydrazine is removed by passing through a hydrazine generator filled with caustic soda (NaOH), which is heated and supplied with steam at 120 ° C from a high pressure boiler. This hydrazine is pyrolyzed in the presence of a palladium catalyst as follows.

Figure kpo00002
Figure kpo00002

상기와 같이 제조된 히드라진의 분해혼합가스(N2: H2=1 : 2)를 폐실리콘유와 접촉시키면 폐실리콘유는 탈산되면서 원상태의 실리콘 화합물로 환원된다.When the decomposition mixture gas (N 2 : H 2 = 1: 2) of the hydrazine prepared as described above is contacted with the waste silicon oil, the waste silicon oil is deoxidized and reduced to the original silicon compound.

이때 히드라진의 열분해반응이 발열반응이고 또 폐실리콘유내의 잔류산소와 미분해 히드라진 가스가 반응하면서 열을 방출하기 때문에 히드라진을 과량 공급하였을 경우 탑내의 온도가 급격한 온도상승으로 인해 히드라진의 용적이 급팽창되어 폭발위험이 생긴다.At this time, the pyrolysis reaction of hydrazine is exothermic and the residual oxygen and undecomposed hydrazine gas in the waste silicon oil reacts to release heat. There is a risk of explosion.

이러한 폭발위험을 방지하기 위해 히드라진의 공급을 폐실리콘유내의 잔류산소와 활성탄중의 과산화수소와 반응할 수 있는 양만 공급해 주는 것이 바람직하며 또이와는 별도로 사전에 질소(N2)가스를 공급해주어야 한다. 상기 공정이 끝나면 탈산된 폐실리콘 처리유는 제올라이트 및 흡착제를 이용하여 각종산류나 분진등을 제거하고 그밖에 불순물이나 수분을 제거한다.In order to prevent the explosion risk, it is desirable to supply the hydrazine supply only with a quantity capable of reacting with residual oxygen in waste silicon oil and hydrogen peroxide in activated carbon, and separately, a nitrogen (N 2 ) gas must be supplied in advance. After the above process, deoxidized waste silicon treated oil is removed from zeolites and adsorbents to remove various acids and dusts and other impurities and water.

본 발명에서 사용되는 흡착제는 활성탄 100중량부에 3% 과산화수소 용액 200중량부를 혼합한 다음 이를 원심분리하여 탈수시킨후 온도 80℃에서 건조시켜 활성탄의 함수비가 5%이내로 건조시킨 것을 사용한다. 흡착제는 폐실리콘유내 존재하는 미생물이나 불순물을 흡착제거해준다. 또한 활성탄중에 함유된 과산화수소는 미분해 히드라진과 반응시켜 히드라진을 제거해주고 폐실리콘중에 잔류하는 산소를 제거해 준다. 이하 본 발명을 첨부된 도면에 의해 설명하면 다음과 같다.The adsorbent used in the present invention is mixed with 100 parts by weight of activated carbon 200 parts by weight of 3% hydrogen peroxide solution and then centrifuged and dehydrated and dried at a temperature of 80 ℃ to use the water content of the activated carbon dried within 5%. The adsorbent absorbs and removes microorganisms and impurities in the waste silicone oil. In addition, hydrogen peroxide contained in activated carbon reacts with undecomposed hydrazine to remove hydrazine and remove oxygen remaining in waste silicon. Hereinafter, the present invention will be described with reference to the accompanying drawings.

수화 히드라진 저장탱크(1)에 잇는 수화 히드라진을 이송펌프(2)에 의해 히드라진 발생탑(3)으로 이송하여 공급해준다. 히드라진 발생탑(3)은 보일러로부터 120℃의 스팀이 가열되어 공급되고 분말상태의 가성소다(NaOH)가 충진되어 있는 처리탑이다. 수화 히드라진은 가성소다가 충진된 처리탑(4)에 통과시키면 수분이 제거되면서 히드라진이 얻어진다. 이 히드라진은 이용펌프(5)를 이용하여 히드라진 저장탱크(6)에 저장한다.The hydrazine hydrazine in the hydrated hydrazine storage tank 1 is transferred to the hydrazine generating tower 3 by a transfer pump 2 and supplied. The hydrazine generating tower 3 is a processing tower in which steam at 120 ° C. is heated and supplied from a boiler and filled with powdered caustic soda (NaOH). Hydrated hydrazine is passed through the treatment tower (4) filled with caustic soda while hydrazine is obtained as water is removed. This hydrazine is stored in the hydrazine storage tank 6 using the use pump 5.

히드라진 저장탱크(6)에 있는 히드라진은 주입펌프(7)을 이용하여 제올라이트 및 파라듐 촉매가 내장된 탈산장치(10)의 반응탑(12)에 주입하면서 보일러(13)120-350℃로 열을 가해주면 히드라진은 질수(N2)와 수소(H2)의 혼합가스로 분해된다.The hydrazine in the hydrazine storage tank 6 is heated to 120-350 ° C. in the boiler 13 while being injected into the reaction tower 12 of the deoxidizer 10 containing the zeolite and palladium catalyst by using the injection pump 7. Hydrazine is decomposed into a mixed gas of nitrogen (N 2 ) and hydrogen (H 2 ).

또한 폐실리콘 저장탱크(8)에 있는 폐실리콘유는 주입펌프(9)에 의해 제올라이트 및 파라듐촉매가 내장되어 있는 탈산장치(10)의 분사탑(11)에 주입 분무한다. 분사탑(11)에 분무된 에어로졸 상태의 폐실리콘유는 하강하면서 파라듐 촉매 존재하에서 반응탑(12)에서 열분해된 히드라진 분해혼합가스와 반응하여 폐실리콘내에 함유되어 있는 산화물을 탈산시켜 원상태로 복귀시킨다. 탈산된 처리유는 반응탑(12) 하부에 있는 제올라이트층을 통과하면서 탈산처리유에 함유된 각종 산류분진등이 여과되고 흡착제인 활성탄에 의해 불순물 및 수분이 제거되므로서 탈산실리콘유를 얻는다. 도면중 미설명부호 14는 이송펌프이고, 15는 재생실리콘 저장탱크이다.In addition, the waste silicon oil in the waste silicon storage tank 8 is injected and sprayed by the injection pump 9 into the injection tower 11 of the deoxidation device 10 in which the zeolite and the palladium catalyst are embedded. The waste silicon oil in the aerosol state sprayed on the injection tower 11 reacts with the hydrazine cracking mixed gas pyrolyzed in the reaction tower 12 in the presence of a palladium catalyst to deoxidize the oxide contained in the waste silicon and return to the original state. Let's do it. The deoxidized treated oil is passed through the zeolite layer under the reaction column 12, and various acid dusts and the like contained in the deoxidized treated oil are filtered and impurities and water are removed by activated carbon as an adsorbent to obtain deoxidized silicone oil. In the figure, reference numeral 14 denotes a transfer pump, and 15 denotes a recycled silicon storage tank.

이상과 같이 본 발명에 의해 제조된 재생실리콘유는 확산진공펌프로 사용되기 전의 실리콘유와 손색이 없는 재생유로 나타났다. 또한 브라운관 배기실험설비 (Doll기)에 브라운관을 부착하고 브라운관 배기용 진공펌프유로 1개월간 시험 사용해본 결과 10-6Torr진공도가 유지됨을 알수 있었다.As described above, the regenerated silicone oil produced by the present invention was found to be a regenerated oil which is not comparable with silicone oil before being used as a diffusion vacuum pump. In addition, a brown tube was attached to the brown tube exhaust test facility (Doll machine) and the vacuum tube for brown tube exhaust was used for 1 month. As a result, 10 -6 Torr vacuum was maintained.

표table

Figure kpo00003
Figure kpo00003

ｏ 시험방법 : KSM 2024(85), 2014(85), 2031(85), 2002(81), 2011(81)에 의함ｏ Test method: According to KSM 2024 (85), 2014 (85), 2031 (85), 2002 (81), 2011 (81)

ｏ 증류시험(종말점)은 400℃이상이므로 C.O.C온도계로 측정불가함.Since distillation test (end point) is over 400 ℃, it cannot be measured by C.O.C thermometer.

ｏ 원유는 일본신에쓰사의 제품임(Hivac 4F)ｏ Crude oil is a product of Nihon Shin-Etsu (Hivac 4F)

Claims (1)

히드라진을 파라듐 촉매 존재하에서 온도 120℃로 열분해시켜 히드라진의 열분해 혼합가스(N2: H2=1 : 2)를 제조한 다음 폐실리콘유를 상기의 히드라진의 열분해 혼합가스와 반응시켜 탈산시키고 이를 다시 제올라이트 및 활성탄을 이용하여 산류분진등의 불순물을 흡착 제거하여 재생시킴을 특징으로 하는 폐실리콘유의 재생방법.Pyrolysis of hydrazine at a temperature of 120 ° C. in the presence of a paradium catalyst to prepare a pyrolysis mixed gas of hydrazine (N 2 : H 2 = 1: 2), followed by deoxidation of the waste silicon oil by reaction with the pyrolysis mixed gas of hydrazine. And regenerating by regenerating by resorbing impurities such as acid dust using zeolite and activated carbon.
KR1019860010983A 1986-12-19 1986-12-19 Reproducing method of wasted silicon oil KR890005042B1 (en)

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KR1019860010983A KR890005042B1 (en) 1986-12-19 1986-12-19 Reproducing method of wasted silicon oil

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KR880007706A KR880007706A (en) 1988-08-29
KR890005042B1 true KR890005042B1 (en) 1989-12-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109468163A (en) * 2018-04-13 2019-03-15 湖北爱国石化有限公司 A kind of purification processing technology of mineral waste feedstock oil

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109468163A (en) * 2018-04-13 2019-03-15 湖北爱国石化有限公司 A kind of purification processing technology of mineral waste feedstock oil

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