KR0184862B1 - Cleaning of equipment used in a liquid phase oxidation process - Google Patents
Cleaning of equipment used in a liquid phase oxidation process Download PDFInfo
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- KR0184862B1 KR0184862B1 KR1019900023035A KR900023035A KR0184862B1 KR 0184862 B1 KR0184862 B1 KR 0184862B1 KR 1019900023035 A KR1019900023035 A KR 1019900023035A KR 900023035 A KR900023035 A KR 900023035A KR 0184862 B1 KR0184862 B1 KR 0184862B1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Treating Waste Gases (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Gas Separation By Absorption (AREA)
Abstract
액상 산화 공정에서 사용되는 장치를 세척하기 위한, 3내지 30 질량%의 아황산의 염, 0.5 내지 30 질량%의 킬레이트화제 및 0.05 내지 5 질량%의 양이온 계면활성제를 함유하는 조성물.A composition containing 3 to 30% by weight of a salt of sulfurous acid, 0.5 to 30% by weight of a chelating agent and 0.05 to 5% by weight of a cationic surfactant for washing the apparatus used in the liquid phase oxidation process.
Description
수성 반응물의 재생과 함께 액상 산화 공정을 위한 플랜트의 구성을 도식적으로 나타낸 것이다.The construction of the plant for the liquid phase oxidation process together with the regeneration of the aqueous reactants is shown schematically.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
도관 : 4,8,9,12,15,24,30,37,38,42Conduit: 4,8,9,12,15,24,30,37,38,42
접촉기 : 6 분리기 : 10Contactor: 6 Separator: 10
산화기 : 19 송풍기 : 23Oxidizer: 19 Blower: 23
순환 펌프 : 27 펌프 : 31Circulation pump: 27 Pump: 31
탱크 : 36 열교환기 : 43Tank: 36 Heat Exchanger: 43
본 발명은 액상 산화 공정에서 사용되는 장치의 세척에 관한 것이다.The present invention relates to the cleaning of apparatus used in liquid phase oxidation processes.
명세서 및 청구범위에서, 액상 산화 공정이라는 용어는, 기체가 황화 수소를 전환시키는 조건하에서 황의 융점 이하의 온도에서 접촉지역 내에서 유기산과 철(Ⅲ)의 가용화된 배위착염을 포함하는 수성 반응물 용액과 접촉되어, 감소된 황화수소 함량을 갖는 처리된 기체 및 고체 황과 증가된 농도의 유기산과 철(Ⅱ)의 가용화된 배위착염을 함유하는 수성 혼합물을 생성하는, 기체로부터 황화 수소를 제거하는 공정을 의미하는데 사용된다.In the specification and claims, the term liquid phase oxidation process refers to an aqueous reactant solution comprising a solubilized coordination salt of organic acid and iron (III) in a contacting zone at temperatures below the melting point of sulfur under conditions in which the gas converts hydrogen sulfide and Contacting to remove hydrogen sulfide from the gas to produce a treated gas having a reduced hydrogen sulfide content and an aqueous mixture containing solid sulfur and an increased concentration of organic acid and solubilized coordination salt of iron (II). It is used to
분리 지역에서, 황은 수성 혼합물로부터 제거되며, 철(Ⅱ)은 철(Ⅲ)로 산화되어 접촉지역에서 사용하기 위한 수성 혼합물을 재생시킨다.In the separation zone, sulfur is removed from the aqueous mixture and iron (II) is oxidized to iron (III) to regenerate the aqueous mixture for use in the contacting zone.
전술한 공정에서 사용되는 장치는, 접촉 지역 내에 형성된 황 원소, 철 반응물과 과량의 황화수소 간의 반응에 의해 형성된 황화 제일철과 수산화철, 및 기체의 업스트림 처리로부터 안개 형태로 이동되는 중 탄화수소의 침전으로 인해 오염되기 쉽다.The apparatus used in the process described above is contaminated due to precipitation of elemental sulfur formed in the contact zone, ferrous sulfide and iron hydroxide formed by the reaction between the iron reactant and excess hydrogen sulfide, and heavy hydrocarbons that are transported in the form of fog from upstream treatment of the gas. Easy to be
수성 반응물 용액을 사용하여 분해되는 황 원소를 자동적으로 제거하고, 계면 활성제를 사용하여 기름막 형성을 막는 것은 공지되어 있다.It is known to use an aqueous reactant solution to automatically remove the elemental sulfur which is decomposed and to prevent the formation of an oil film using a surfactant.
본 발명의 목적은 전술한 세 형태의 오염을 효과적으로 막을 수 있는 액상 산화 공정에서 사용되는 장치를 세척하기 위한 조성물을 제공하는 것이다.It is an object of the present invention to provide a composition for cleaning a device used in a liquid oxidation process which can effectively prevent the three types of contamination mentioned above.
이러한 목적을 위해서 본 발명에 따라 액상 산화 공정에서 사용되는 장치의 세척을 위한 조성물은 아황산의 염 3 내지 30 질량%, 킬레이트화제 0.5 내지 30 질량% 및 양이온 계면 활성제 0.05 내지 5질량%의 수용액으로 구성된다.For this purpose the composition for washing of the apparatus used in the liquid oxidation process according to the invention consists of an aqueous solution of 3 to 30 mass% of salts of sulfurous acid, 0.5 to 30 mass% of chelating agents and 0.05 to 5 mass% of cationic surfactants. do.
아황산염은 아황산염 또는 아황산수소염일 수 있다. 아황산염 (또는 아황산수소염)은 황원소와 함께 물에 용해될 수 있는 티오술페이트를 형성할 것이다.The sulfite may be sulfite or hydrogen sulfite. Sulfite (or hydrogen sulfite) will form thiosulfate that can be dissolved in water with elemental sulfur.
불용성 황화제일철과 수산화철은 철이 조합된 분자 구조를 형성하는 킬레이트화제에 의해 용해된다.Insoluble iron sulfide and iron hydroxide are dissolved by chelating agents to form a molecular structure in which iron is combined.
양이온 계면활성제는 기름 제거를 촉진할 것이다. 그러나, 양이온 계면활성제는 아황산염 (또는 아황산수소염)과 황 사이의 티오술페이트로의 반응 및, 수산화철의 용해에 더욱 유리한 영향을 미친다.Cationic surfactants will promote oil removal. However, cationic surfactants have a more favorable effect on the reaction of sulfites (or hydrogen sulfite) with sulfur to thiosulfate and the dissolution of iron hydroxide.
본 발명의 잇점은, 세척 조성물 내에 용해된 오염물을 갖는 세척 조성물은 수성 반응물 용액과 양립할 수 있는 무해한 물질을 함유하는 것이다.An advantage of the present invention is that cleaning compositions having contaminants dissolved in the cleaning composition contain harmless substances that are compatible with the aqueous reactant solution.
적절하게는 아황산염은 암모늄염 또는 나타륨 염이다.Suitably the sulfite is an ammonium salt or a natrium salt.
킬레이트화제는 유기산 또는 암모늄염 또는 나트륨염 같은 유기산의 염일 수 있다. 유기산은 적절하게는, 니트릴로트리아세트산(NTA로 명명함), 에틸렌디아민테트라아세트산(EDTA로 명명함)또는 히드록시에틸렌디아민트리에세트산(HOEDTA로 명명함)같은 질소 다중산이다.Chelating agents may be salts of organic acids or organic acids such as ammonium or sodium salts. The organic acid is suitably nitrogen polyacid, such as nitrilotriacetic acid (named NTA), ethylenediaminetetraacetic acid (named EDTA) or hydroxyethylenediaminetriacetic acid (named HOEDTA).
적절하게는 아황산의 염 내 양이온은 킬레이트화제에 속한 양이온과 같다. 또한, 세척 조성물의 킬레이트화제는 적절하게는 액상 산화 공정에서 사용되는 킬레이트화제와 같다.Suitably the cation in the salt of sulfurous acid is the same as the cation belonging to the chelating agent. In addition, the chelating agent of the cleaning composition is suitably the same as the chelating agent used in the liquid oxidation process.
양이온 계면활성제는 적절하게는 4차 암모늄염, 예컨대 디알킬디메틸암모늄염, 알키벤질디메틸암모늄 할라이드 같은 알킬 벤질 디메틸 암모늄 할라이드, 알킬트리메틸 암모늄염, 또는 도데실 피리디늄 브로마이드 같은 알킬피리디늄 할라이드이다.Cationic surfactants are suitably quaternary ammonium salts such as dialkyldimethylammonium salts, alkyl benzyl dimethyl ammonium halides such as alkybenzyldimethylammonium halides, alkyltrimethyl ammonium salts, or alkylpyridinium halides such as dodecyl pyridinium bromide.
본 발명에 따른 조성물을 오염된 장치와 접촉시키는 것은 10 내지 80℃온도에서 수행된다.Contacting the composition according to the invention with a contaminated device is carried out at a temperature of 10 to 80 ° C.
이제 본 발명은 수성 반응물의 재생과 함께 액상 산화 공정을 위한 플랜트의 구성을 도식적으로 나타낸 첨부 도면을 참조로 하여 실시예에 의해 보다 상세히 설명될 것이다. 점선은 액상 산화 공정에서 사용되는 도관을 나타내며, 실선은 액상 산화 공정에서 사용되는 장치를 세척할 때 사용되는 도관을 나타낸다.The invention will now be described in more detail by way of examples with reference to the accompanying drawings which schematically show the construction of a plant for liquid phase oxidation with the regeneration of aqueous reactants. The dashed line represents the conduit used in the liquid phase oxidation process, and the solid line represents the conduit used when cleaning the device used in the liquid phase oxidation process.
황화 수소가 제거되는 가스는 상승 압력에서 도관(4)를 통해 병존하는 접촉기(6)으로 공급되고, 수성 반응물 용액은 도관(8)을 통해 병존하는 접촉기(6)에 공급된다. 반응물 용액은 NTA와 철의 가용화된 배위 착염을 함유한다. 황화수소를 황원소로 전환시키는 조건하에서 ,가스와 반응물 용액은 접촉기(6)내에서 접촉하여, 감소된 황화수소 함량을 갖는 처리 기체 및, 고체 황과 증가된 용도의 NTA와 철(Ⅱ)의 가용화된 배위착염을 함유하는 수성 혼합물을 생성한다. 기체/액체 혼합물은 병존하는 접촉기(6)으로 부터 도관(9)를 통해, 기체/액체 분리기(10)으로 통과하고, 이로부터 처리된 기체가 도관(12)를 통해 제거되고 고체 황과 증가된 농도의 NTA와 철(Ⅱ)의 가용화된 배위착염을 함유하는 수성 혼합물이 도관(15)를 통해 제거된다.The gas from which the hydrogen sulfide is removed is fed through the conduit 4 to the existing contactor 6 at elevated pressure, and the aqueous reactant solution is fed through the conduit 8 to the existing contactor 6. The reactant solution contains solubilized coordination salts of NTA and iron. Under conditions of converting hydrogen sulfide to sulfur element, the gas and reactant solution are contacted in the contactor 6 to solubilize the treating gas with reduced hydrogen sulfide content and solid sulfur with increased use of NTA and iron (II). An aqueous mixture containing coordinating salts is produced. The gas / liquid mixture passes from concomitant contactor 6 through conduit 9 and into gas / liquid separator 10, from which treated gas is removed through conduit 12 and increased with solid sulfur. An aqueous mixture containing a concentration of NTA and solubilized coordination salts of iron (II) is removed via conduit 15.
수성 혼합물은 환원된 철(Ⅱ)이 공기에 의해 철(Ⅲ)으로 산화되는 산화기(19)의 상부에 도관(15)를 통해 공급되고, 송풍기(23)에 의해 도관(24)를 경유하여 산화기(19)의 하부로 공급된다. 환원된 반응물을 산화시키는 조건은 본 발명과는 관련이 없다.The aqueous mixture is supplied via conduit 15 to the top of the oxidizer 19 where reduced iron (II) is oxidized to iron (III) by air, and via blower 23 via conduit 24. Fed to the bottom of the oxidizer 19. Conditions for oxidizing the reduced reactant are not relevant to the present invention.
재생된 반응물은 도관(26)을 통해 산화기(19)로부터 회수되고, 순환펌프(27)에 의해 도관(8)을 통하여 병존하는 접촉기(6)으로 공급된다.The regenerated reactant is withdrawn from the oxidizer 19 via conduit 26 and fed by a circulating pump 27 to the contactor 6 which coexists via conduit 8.
산화기(19)의 바닥으로부터 황이 풍부한 슬러리가, 용액이 펌프(31)에 의해 황을 더 처리하고 저장하기 위한 장치(도시되지 않음)로 공급되는 도관(30)을 통해 회수된다. 감손 공기는 도관(35)를 통해 산화기(19)의 최상단을 떠난다.Sulfur-rich slurry from the bottom of the oxidizer 19 is recovered through a conduit 30 where the solution is fed by a pump 31 to an apparatus (not shown) for further treatment and storage of sulfur. Depleted air leaves the top of oxidizer 19 through conduit 35.
전술한 공정에 사용되는 장치를 세척하기 위해서, 이 공정을 중단하고, 접촉기를 감압하고, 세척 조성물을 순환 펌프(27)에 의해 탱크(36)으로부터 도관(37)과 (38)을 통해서 병존 접촉기(6)을 보내고, 그곳으로부터 다시 도관(42)를 통해 탱크(36)으로 보낸다. 사용되는 세척 조성물은 10질량%의 암모늄 술파이트, 10 질량%의 암모늄 NTA 및 0.1 질량%의 도데실 피리디늄 브로마이드를 함유한다. 세척 조성물은 열교환기(43)에 의해 도관(38)내에서 60℃온도로 가열된다.In order to clean the apparatus used in the above-described process, this process is stopped, the contactor is depressurized, and the cleaning composition is passed through the conduit 37 and 38 from the tank 36 by means of the circulation pump 27 through the conduits 37 and 38. (6) is sent from there back through the conduit (42) to the tank (36). The wash composition used contains 10% by weight of ammonium sulfite, 10% by weight of ammonium NTA and 0.1% by weight of dodecyl pyridinium bromide. The cleaning composition is heated to a 60 ° C. temperature in conduit 38 by heat exchanger 43.
세척이 완료될 때, 조성물을 탱크로 빼내고, 깨끗한 병존 접촉기(6)을 서어비스로 취한다.When the wash is complete, the composition is taken out of the tank and the clean coordinating contactor 6 is taken as a service.
보다 명확하게 하기 위해, 세척 조성물이 통과하는 도관 시스템을 수성 반응물 용액이 통과하는 도관 시스템으로부터 분리시켜 나타낸다. 그러나, 조성물이 통과하는 도관 시스템 내에, 정상적인 작동 중 수성 반응물 용액이 통과하는 도관들이 포함되는 것으로 이해될 것이다. 이 방법으로 순환펌프(27)뿐 아니라 도관 시스템의 부품들이 또한 세척된다.For clarity, the conduit system through which the cleaning composition passes is shown separate from the conduit system through which the aqueous reactant solution passes. However, it will be understood that within the conduit system through which the composition passes, conduits through which the aqueous reactant solution passes during normal operation are included. In this way the components of the conduit system as well as the circulation pump 27 are also cleaned.
적절하게는 플랜트가 가진 두개의 병존 접촉기 및 이에 속하는 순환펌프를 포함하고 있으므로, 세척되고 있는 접촉기로부터 서어비스를 받을 수 있는 병존 접촉기가 존재한다.As there are suitably two parallel contactors with the plant and a circulating pump belonging to them, there is a parallel contactor capable of receiving service from the contactor being cleaned.
Claims (6)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL90000282 | 1990-01-02 | ||
| GB909000028A GB9000028D0 (en) | 1990-01-02 | 1990-01-02 | Cleaning of equipment used in a liquid phase oxidation process |
| GB9000282 | 1990-01-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR910014497A KR910014497A (en) | 1991-08-31 |
| KR0184862B1 true KR0184862B1 (en) | 1999-04-15 |
Family
ID=10668753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019900023035A KR0184862B1 (en) | 1990-01-02 | 1990-12-31 | Cleaning of equipment used in a liquid phase oxidation process |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0438833B1 (en) |
| JP (1) | JP2832493B2 (en) |
| KR (1) | KR0184862B1 (en) |
| AU (1) | AU624756B2 (en) |
| CA (1) | CA2031874C (en) |
| DE (1) | DE69026063T2 (en) |
| ES (1) | ES2084653T3 (en) |
| GB (1) | GB9000028D0 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6872747B2 (en) * | 2017-01-17 | 2021-05-19 | 株式会社片山化学工業研究所 | Sulfur scale cleaning agent and sulfur scale cleaning method using it |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5471787A (en) * | 1977-11-18 | 1979-06-08 | Kiresuto Giken Kk | Ironnremoving detergent for cation exchange resin |
| SE8204843L (en) * | 1982-01-18 | 1983-07-19 | Dearborn Chemicals Co | purification process |
| GB8506685D0 (en) * | 1985-03-14 | 1985-04-17 | Unilever Plc | Laundry bars |
| GB8619391D0 (en) * | 1986-08-08 | 1986-09-17 | Unilever Plc | Acidic liquid cleaning composition |
-
1990
- 1990-01-02 GB GB909000028A patent/GB9000028D0/en active Pending
- 1990-12-10 CA CA002031874A patent/CA2031874C/en not_active Expired - Fee Related
- 1990-12-14 AU AU68133/90A patent/AU624756B2/en not_active Ceased
- 1990-12-20 DE DE69026063T patent/DE69026063T2/en not_active Expired - Fee Related
- 1990-12-20 ES ES90203478T patent/ES2084653T3/en not_active Expired - Lifetime
- 1990-12-20 EP EP90203478A patent/EP0438833B1/en not_active Expired - Lifetime
- 1990-12-28 JP JP2415515A patent/JP2832493B2/en not_active Expired - Lifetime
- 1990-12-31 KR KR1019900023035A patent/KR0184862B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE69026063T2 (en) | 1996-08-29 |
| ES2084653T3 (en) | 1996-05-16 |
| GB9000028D0 (en) | 1990-03-07 |
| EP0438833A1 (en) | 1991-07-31 |
| AU624756B2 (en) | 1992-06-18 |
| AU6813390A (en) | 1991-07-04 |
| DE69026063D1 (en) | 1996-04-25 |
| JP2832493B2 (en) | 1998-12-09 |
| CA2031874C (en) | 2000-10-10 |
| JPH04145199A (en) | 1992-05-19 |
| CA2031874A1 (en) | 1991-07-03 |
| EP0438833B1 (en) | 1996-03-20 |
| KR910014497A (en) | 1991-08-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| LAPS | Lapse due to unpaid annual fee |