EP0438833B1 - Cleaning of equipement used in a liquid phase oxidation process - Google Patents
Cleaning of equipement used in a liquid phase oxidation process Download PDFInfo
- Publication number
- EP0438833B1 EP0438833B1 EP90203478A EP90203478A EP0438833B1 EP 0438833 B1 EP0438833 B1 EP 0438833B1 EP 90203478 A EP90203478 A EP 90203478A EP 90203478 A EP90203478 A EP 90203478A EP 0438833 B1 EP0438833 B1 EP 0438833B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- liquid phase
- oxidation process
- phase oxidation
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to cleaning of equipment as used in a liquid oxidation process.
- liquid phase oxidation process refers to a process for removing hydrogen sulphide from a gas wherein the gas is contacted with an aqueous reactant solution in a contacting zone at a temperature below the melting point of sulphur, the reactant solution including solubilized coordination complex of iron (III) with an organic acid, under conditions to convert hydrogen sulphide, producing a treated gas having reduced hydrogen sulphide content, and aqueous mixture containing solid sulphur and an increased concentration of solubilized coordination complex of iron (II) with the organic acid.
- sulphur 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.
- Equipment used in the above described process is subject to fouling caused by deposition of elemental sulphur formed in the contacting zone; iron sulphide and iron hydroxide formed by a reaction between the reactant iron and an excess amount of hydrogen sulphide; and heavy hydrocarbons which are carried over as mist from upstream treating of the gas.
- composition for cleaning equipment used in a liquid phase oxidation process comprises an aqueous solution of between 3 and 30 %mass of a salt of sulphurous acid, between 0.5 and 30 %mass of a chelating agent and between 0.05 and 5 %mass of a cationic surfactant.
- the salt of sulphurous acid can be a sulphite or a bisulphite.
- the sulphite (or bisulphite) will form with elemental sulphur a thiosulphate which is soluble in water.
- Insoluble iron sulphide and iron hydroxide are dissolved by means of the chelating agent which forms molecular structures in which iron ions are combined.
- the cationic surfactant will facilitate removing oil.
- the cationic surfactant has moreover a beneficial effect on the reaction between sulphite (or bisulphite) and sulphur to thiosulphate and on the dissolution of iron hydroxide.
- An advantage of the present invention is that the cleaning composition with the contaminants dissolved in it contains innocuous matter that is compatible with the aqueous reactant solution.
- the salt of sulphurous acid is the ammonium salt or a sodium salt.
- the chelating agent can be an organic acid or a salt of an organic acid such as the ammonium salt or the sodium salt.
- the organic acid is suitably a nitrogeneous polyacid, such as nitrilotriacetic acid (to be referred to as NTA), ethylenediaminetetraacetic acid (to be referred to as EDTA) or hydroxyethylenediaminetriacetic acid (to be referred to as HOEDTA).
- the cation in the salt of the sulphurous acid is the same as the cation pertaining to the chelating agent.
- the chelating agent of the cleaning composition is suitably the same as the chelating agent used in the liquid phase oxidation process.
- the cationic surfactant is suitably a quaternary ammonium salt for example a dialkyldimethylammonium salt, an alkylbenzyldimethyl ammonium halide such as an alkybenzyldimethyl ammonium halide, an alkyltrimethylammonium salt or an alkylpyridinium halide such as dodecyl pyridinium bromide.
- a quaternary ammonium salt for example a dialkyldimethylammonium salt, an alkylbenzyldimethyl ammonium halide such as an alkybenzyldimethyl ammonium halide, an alkyltrimethylammonium salt or an alkylpyridinium halide such as dodecyl pyridinium bromide.
- Contacting the fouled equipment with the composition according to the present invention is carried out at a temperature between 10 and 80 °C.
- Gas from which hydrogen sulphide is to be removed is supplied at elevated pressure through conduit 4 to co-current contactor 6, and aqueous reactant solution is supplied to the co-current contactor 6 through conduit 8.
- the reactant solution contains solubilized coordination complex of iron(III) with NTA.
- gas and reactant solution are contacted in contactor 6 to produce a treated gas having reduced hydrogen sulphide content and aqueous mixture containing solid sulphur and an increased concentration of solubilized coordination complex of iron(II) with NTA.
- the gas/liquid mixture is passed through conduit 9 from the co-current contactor 6 to a gas/liquid separator 10 from which treated gas is removed through conduit 12 and aqueous mixture containing solid sulphur and an increased concentration of solubilized coordination complex of iron(II) with NTA through conduit 15.
- the aqueous mixture is supplied through conduit 15 to the upper part of oxidizer 19 in which reduced iron (II) is oxidized to iron(III) by means of air, supplied by blower 23 through conduit 24 to the lower part of oxidizer 19.
- reduced iron (II) is oxidized to iron(III) by means of air, supplied by blower 23 through conduit 24 to the lower part of oxidizer 19.
- the conditions for oxidizing reduced reactant are not relevant to the present invention.
- Regenerated reactant is withdrawn from the oxidizer 19 through conduit 26 and is supplied by circulation pump 27 through conduit 8 to the co-current contactor 6.
- a sulphur-rich slurry is withdrawn through conduit 30 which solution is supplied by pump 31 to means for further treating sulphur and storing the sulphur (not shown). Depleted air leaves the top of the oxidizer 19 through conduit 35.
- this process is interrupted, the contactor is depressurized and cleaning composition is passed from tank 36 by circulation pump 27 through conduits 37 and 38 to the co-current contactor 6 and from there back to the tank 36 through conduit 42.
- the cleaning composition used contains 10 %mass of ammonium sulphite, 10 %mass of ammonium NTA and 0.1 %mass of dodecyl pyridinium bromide.
- the cleaning composition is heated by heat-exchanger 43 in conduit 38 to a temperature of 60 °C.
- the composition is drained to the tank and the clean co-current contactor 6 is taken into service.
- conduit system through which the cleaning composition is passed is shown separately from the conduit system through which the aqueous reactant solution is passed.
- conduits are included through which during normal operation aqueous reactant solution passes. In this way in addition to circulation pump 27 parts of the conduit system are cleaned as well.
- the plant includes two co-current contactors with circulation pumps belonging thereto, so that there is a co-current contactor which can take over service from the contactor that is being cleaned.
Landscapes
- Chemical & Material Sciences (AREA)
- 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)
- Gas Separation By Absorption (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB909000028A GB9000028D0 (en) | 1990-01-02 | 1990-01-02 | Cleaning of equipment used in a liquid phase oxidation process |
GB9000028 | 1990-01-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0438833A1 EP0438833A1 (en) | 1991-07-31 |
EP0438833B1 true EP0438833B1 (en) | 1996-03-20 |
Family
ID=10668753
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90203478A Expired - Lifetime EP0438833B1 (en) | 1990-01-02 | 1990-12-20 | Cleaning of equipement used in a liquid phase oxidation process |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0438833B1 (ja) |
JP (1) | JP2832493B2 (ja) |
KR (1) | KR0184862B1 (ja) |
AU (1) | AU624756B2 (ja) |
CA (1) | CA2031874C (ja) |
DE (1) | DE69026063T2 (ja) |
ES (1) | ES2084653T3 (ja) |
GB (1) | GB9000028D0 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6872747B2 (ja) * | 2017-01-17 | 2021-05-19 | 株式会社片山化学工業研究所 | 硫黄スケールの洗浄剤およびそれを用いる硫黄スケールの洗浄方法 |
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 (sv) * | 1982-01-18 | 1983-07-19 | Dearborn Chemicals Co | Reningsforfarande |
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 EP EP90203478A patent/EP0438833B1/en not_active Expired - Lifetime
- 1990-12-20 ES ES90203478T patent/ES2084653T3/es not_active Expired - Lifetime
- 1990-12-20 DE DE69026063T patent/DE69026063T2/de not_active Expired - Fee Related
- 1990-12-28 JP JP2415515A patent/JP2832493B2/ja not_active Expired - Lifetime
- 1990-12-31 KR KR1019900023035A patent/KR0184862B1/ko not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DE69026063D1 (de) | 1996-04-25 |
ES2084653T3 (es) | 1996-05-16 |
CA2031874A1 (en) | 1991-07-03 |
KR0184862B1 (ko) | 1999-04-15 |
AU624756B2 (en) | 1992-06-18 |
AU6813390A (en) | 1991-07-04 |
CA2031874C (en) | 2000-10-10 |
JP2832493B2 (ja) | 1998-12-09 |
JPH04145199A (ja) | 1992-05-19 |
DE69026063T2 (de) | 1996-08-29 |
EP0438833A1 (en) | 1991-07-31 |
GB9000028D0 (en) | 1990-03-07 |
KR910014497A (ko) | 1991-08-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4784775A (en) | Removal of hydrogen sulfide from sour water | |
US4374104A (en) | Composition and method for removing hydrogen sulfide from gas stream | |
CA1180536A (en) | Removal of hydrogen sulfide from fluid streams with minimum production of solids | |
US4468929A (en) | Purifying geothermal steam | |
JPH0587290B2 (ja) | ||
JP2021502896A (ja) | 液化ガスの脱メルカプタンによるアルカリ液の再生方法 | |
WO2003013701A1 (en) | Method and apparatus for nox and so2 removal | |
RU2103050C1 (ru) | Способ селективного удаления сульфида водорода из газа и устройство для его осуществления | |
EP0438833B1 (en) | Cleaning of equipement used in a liquid phase oxidation process | |
JPS6010773B2 (ja) | ガスから硫化水素の除去 | |
WO2016063581A1 (ja) | アンモニア含有排水の処理方法および処理装置 | |
DE60109565T2 (de) | Verfahren zur Reinigung von Schwefel | |
JPS58152488A (ja) | 硫化水素の除去方法 | |
US5912387A (en) | Amine heat stable salt neutralization having reduced solids | |
WO2001066235A1 (en) | Process for purifying aqueous buffer solutions | |
US5866089A (en) | Ultrasound-assisted liquid redox absorber | |
JPS6357799A (ja) | メツキ液の処理方法 | |
US5979470A (en) | Method for on-line cleaning of sulfur deposits | |
JPS6020437B2 (ja) | 硫化水素を粗コ−クス炉ガスから除去する方法及び装置 | |
JPS60257822A (ja) | 硫化水素の除去方法 | |
EP0141872B1 (en) | Removal of hydrogen sulfide from steam | |
US5695727A (en) | Process for removing sulfur dioxide and nitrogen oxides from a hot gaseous stream with ferrous chelate regeneration | |
JP3669872B2 (ja) | 灰の処理方法 | |
WO2005053820A1 (en) | Desulfurization of gases for gaseous fuels treatment or odour control | |
JPH07114959B2 (ja) | 活性炭触媒の再生方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE ES FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19911206 |
|
17Q | First examination report despatched |
Effective date: 19941025 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES FR GB IT NL |
|
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI & PERANI S.P.A. |
|
REF | Corresponds to: |
Ref document number: 69026063 Country of ref document: DE Date of ref document: 19960425 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2084653 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20001025 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20001128 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20001208 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20001218 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20001221 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20010115 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011220 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011231 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
BERE | Be: lapsed |
Owner name: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. Effective date: 20011231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020702 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20011220 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020830 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20020701 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021221 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20030113 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051220 |