NO870352L - PROCEDURE FOR HYDROGEN SULFIDE REMOVAL. - Google Patents
PROCEDURE FOR HYDROGEN SULFIDE REMOVAL.Info
- Publication number
- NO870352L NO870352L NO870352A NO870352A NO870352L NO 870352 L NO870352 L NO 870352L NO 870352 A NO870352 A NO 870352A NO 870352 A NO870352 A NO 870352A NO 870352 L NO870352 L NO 870352L
- Authority
- NO
- Norway
- Prior art keywords
- compound
- hydrogen
- raw material
- oil
- hydrogen sulphide
- Prior art date
Links
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000010779 crude oil Substances 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- -1 aromatic isocyanate Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical group O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 22
- 239000003921 oil Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 239000012459 cleaning agent Substances 0.000 description 7
- 239000011435 rock Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for fjerning av hydrogensulfid fra råolje. The present invention relates to a method for removing hydrogen sulphide from crude oil.
Et petroleumreservoar er dannet av et hensiktsmessig formet, porøst lag av bergartmateriale forseglet med en ugjennom-trengelig bergart. Typen av reservoar-bergartmateriale er meget viktig siden oljen er til stede i de små rommene eller porene som adskiller de individuelle bergartkornene. A petroleum reservoir is formed by an appropriately shaped, porous layer of rock material sealed with an impermeable rock. The type of reservoir rock material is very important since the oil is present in the small spaces or pores that separate the individual rock grains.
Råolje finnes generelt i et reservoar i forbindelse med vann, som ofte er saltholdig, og gass. Avhengig av råoljens egen-skaper, temperaturen og trykket, kan gassen forekomme i opp-løsning i oljen eller i tillegg som en separat fase i form av en gasskappe. Oljen og gassen opptar den øvre delen av reservoaret, og under kan det være et betydelig volum vann, kjent som vannreservoaret, som strekker seg gjennom alle bergartmaterialets nedre nivåer. Crude oil is generally found in a reservoir in association with water, which is often saline, and gas. Depending on the properties of the crude oil, the temperature and the pressure, the gas can occur in solution in the oil or in addition as a separate phase in the form of a gas mantle. The oil and gas occupy the upper part of the reservoir, and underneath there may be a significant volume of water, known as the water reservoir, which extends through all the lower levels of the rock material.
For at olje skal bevege seg gjennom porene i reservoar-bergartmaterialet og inn i en brønn, må trykket under hvilket oljen befinner seg i reservoaret, være større enn trykket ved brønnen. For oil to move through the pores in the reservoir rock material and into a well, the pressure under which the oil is in the reservoir must be greater than the pressure at the well.
Vannet som inneholdes i vannreservoaret, er under trykk, og er en drivkilde. Den oppløste gassen forbundet med oljen er en annen, og dette gjelder også den frie gassen i gasskappen når denne er til stede. The water contained in the water reservoir is under pressure and is a driving source. The dissolved gas associated with the oil is another, and this also applies to the free gas in the gas jacket when this is present.
Når olje produseres fra en brønn, presses den fra reservoaret av naturlig trykk til bunnen av brønnen og stiger opp gjennom denne til overflaten. Etter hvert som oljen stiger, blir trykket mindre, og gass forbundet med oljen blir gradvis fri-gjort fra oppløsning. When oil is produced from a well, it is pushed from the reservoir by natural pressure to the bottom of the well and rises through it to the surface. As the oil rises, the pressure decreases, and gas associated with the oil is gradually released from solution.
Etter å ha kommet ut av brønnen er det nødvendig å behandle flerfaseblåndingen av olje, gass og eventuelt vann, i det følgende betegnet "produsert brønnfluid" i separatorer for å fjerne fri eller potensielt fri gass, hovedsakelig metan og etan. Med potensielt fri gass menes gass som det er sannsyn-lig vil komme ut av oppløsning dersom oljen holdes ved om-kring atmosfæretrykk, f.eks. under transport i et tankskip eller i lagringstanker, uten behandling. After coming out of the well, it is necessary to treat the multiphase mixture of oil, gas and possibly water, hereinafter referred to as "produced well fluid" in separators to remove free or potentially free gas, mainly methane and ethane. By potentially free gas is meant gas that is likely to come out of solution if the oil is kept at around atmospheric pressure, e.g. during transport in a tanker or in storage tanks, without treatment.
Noen råoljer inneholder ikke bare oppløste hydrokarbongasser, men også betydelige mengder hydrogensulfid. Dette problemet er særlig forbundet med "utvannede" reservoarer som nærmer seg slutten av deres levetid, skjønt det er ikke begrenset til disse. Some crude oils contain not only dissolved hydrocarbon gases but also significant amounts of hydrogen sulphide. This problem is particularly associated with, although not limited to, "watered down" reservoirs nearing the end of their life.
Hydrogensulfid er en toksisk, illeluktende og korroderende gass og er uakseptabel i mengde fra både sikkerhets- og miljømessige betraktninger. Når hydrogensulfid er til stede, er det nødvendig å tilveiebringe ytterligere behandling for å redusere konsentrasjonen av hydrogensulfid i alle produkter til et akseptabelt lavt nivå. Hydrogen sulphide is a toxic, malodorous and corrosive gas and is unacceptable in quantity from both safety and environmental considerations. When hydrogen sulfide is present, it is necessary to provide additional treatment to reduce the concentration of hydrogen sulfide in all products to an acceptably low level.
Mye av hydrogensulfidet forbinder seg med gassene som resulterer fra gass-olje-separeringsprosessen, og dette kan fjernes ved vasking av gassene, f.eks. med aminer. Dette krever kostbare gass/væske-kontakt-, —regenererings- og —omdannelsesanlegg. Omkostningene for denne ekstra behandling er betydelig og i noen tilfeller, f.eks. offshore-felter, kan det være at gassvasklng ikke er gjennomførlig fordi plass ikke er tilgjengelig på feltplattformene for til-pasning av det nødvendige utstyr. Much of the hydrogen sulfide associates with the gases resulting from the gas-oil separation process, and this can be removed by washing the gases, e.g. with amines. This requires expensive gas/liquid contact, regeneration and conversion facilities. The costs for this additional treatment are significant and in some cases, e.g. offshore fields, it may be that gas washing is not feasible because space is not available on the field platforms for fitting the necessary equipment.
Selv når gassvasking er mulig, etterlater dette imidlertid fremdeles noe hydrogensulfid forbundet med oljefasen og den vandige fasen. However, even when gas scrubbing is possible, this still leaves some hydrogen sulfide associated with the oil phase and the aqueous phase.
Det ville klart være hensiktsmessig å behandle den produserte brønnfluiden med et rensemiddel for hydrogensulfid før de forskjellige fasene separeres. It would clearly be appropriate to treat the produced well fluid with a cleaning agent for hydrogen sulphide before the different phases are separated.
Man har nå oppdaget at visse forbindelser inneholdende til-støtende dobbeltbindinger er i stand til å reagere med hydrogensulfid under blandet fase-betingelser og danne relativt uskadelige tiolforbindelser. It has now been discovered that certain compounds containing adjacent double bonds are capable of reacting with hydrogen sulphide under mixed phase conditions to form relatively harmless thiol compounds.
Ifølge foreliggende oppfinnelse er det således tilveiebragt en fremgangsmåte for rensing av hydrogensulfid fra et råmateriale omfattende råolje og hydrogensulfid, hvilken fremgangsmåte er kjennetegnet ved at man tilsetter en forbindelse med den generelle formel: According to the present invention, there is thus provided a method for purifying hydrogen sulphide from a raw material comprising crude oil and hydrogen sulphide, which method is characterized by adding a compound with the general formula:
hvor R<1>er en alkylgruppe inneholdende 1-18 karbonatomer, en cykloalkyl- eller alkylcykloalkylgruppe inneholdende 3-18 karbonatomer, en arylgruppe, en alkylarylgruppe hvor alkyldelen inneholder 1-18 karbonatomer eller et hydrogenatom, X er et nltrogenatom eller et oksygenatom, og R^ er R-1- når X er et nltrogenatom, eller 0 når X er et oksygenatom, til råmaterialet og lar forbindelsen reagere med hydrogensulfidet som inneholdes deri. Foretrukne forbindelser er isocyanater, mest foretrukket aromatiske isocyanater og diisocyanater. where R<1> is an alkyl group containing 1-18 carbon atoms, a cycloalkyl or alkylcycloalkyl group containing 3-18 carbon atoms, an aryl group, an alkylaryl group where the alkyl part contains 1-18 carbon atoms or a hydrogen atom, X is a nitrogen atom or an oxygen atom, and R^ is R-1- when X is a nitrogen atom, or 0 when X is an oxygen atom, to the raw material and allows the compound to react with the hydrogen sulfide contained therein. Preferred compounds are isocyanates, most preferably aromatic isocyanates and diisocyanates.
Råmaterialet kan være produsert brønnfluid som definert ovenf or. The raw material can be produced well fluid as defined above.
Selvom de ovenfor definerte rensemidlene er særlig nyttige ved behandling av produserte brønnfluider fordi de kan motstå de sistnevntes strenge miljø, er de også egnet for behandling av råolje- og petroleumfraksjoner under mildere betingelser, f.eks. i rørledninger, lagringstanker, jernbanevogner, tankskip osv., etter at den produserte brønnfluiden har blitt avvannet og avgasset. Although the cleaning agents defined above are particularly useful when treating produced well fluids because they can withstand the harsh environment of the latter, they are also suitable for treating crude oil and petroleum fractions under milder conditions, e.g. in pipelines, storage tanks, railcars, tankers, etc., after the produced well fluid has been dewatered and degassed.
Når vannet er til stede, avhenger skillingen av hydrogensulfid mellom de forskjellige fasene stort sett av pH-verdien og redoks-potensialet til den vandige fasen. Disse vil normalt være slik at hydrogensulfidet er konsentrert i oljefasen og den vandige fasen, dvs. i områdene 4-9,5 og fra —0,2 til —0,3 V med hensyn til hydrogenpotensialet, respek-tivt . When water is present, the separation of hydrogen sulphide between the different phases largely depends on the pH value and the redox potential of the aqueous phase. These will normally be such that the hydrogen sulphide is concentrated in the oil phase and the aqueous phase, i.e. in the ranges 4-9.5 and from -0.2 to -0.3 V with respect to the hydrogen potential, respectively.
Rensemidlene er fortrinnsvis oljeoppløselige og reagerer med hydrogensulfidet i oljefasen. Ved masseoverføring reduserer dette også konsentrasjonen av hydrogensulfid i gassfasen og den vandige fasen. De oljeoppløselige rensemidlene bør også være stabile i nærvær av vann og termisk stabile fordi brønn-fluider ofte produseres ved forhøyet temperatur. The cleaning agents are preferably oil-soluble and react with the hydrogen sulphide in the oil phase. In the case of mass transfer, this also reduces the concentration of hydrogen sulphide in the gas phase and the aqueous phase. The oil-soluble cleaning agents should also be stable in the presence of water and thermally stable because well fluids are often produced at elevated temperatures.
Egnede rensemidler omfatter:Suitable cleaning agents include:
Rensemiddelet anvendes hensiktsmessig i en mengde på 1-50, fortrinnsvis 5-15, ganger mengden av tilstedeværende hydrogensulfid, på en molarbasis. The cleaning agent is suitably used in an amount of 1-50, preferably 5-15, times the amount of hydrogen sulphide present, on a molar basis.
Tiden som skal til for å utrense hydrogensulfidet, er fortrinnsvis av størrelsesorden 1-15 minutter. The time required to purify the hydrogen sulphide is preferably of the order of 1-15 minutes.
Oppfinnelsen illustreres under henvisning til følgende eksempler. The invention is illustrated with reference to the following examples.
Eksempler 1- 5Examples 1-5
En kolbe ble tilført 30 g råolje (fra Welton-oljefeltet i Midt-England) og 8 g vann, bufret til en pH-verdi på 7, og forseglet. 2 ml 0,7$ Na2S.9H20 ble deretter innført ved hjelp av en sprøyte, hvilket ga et potensielt B^S-innhold på 0,02 g. A flask was charged with 30 g of crude oil (from the Welton oil field in central England) and 8 g of water, buffered to a pH of 7, and sealed. 2 mL of 0.7% Na 2 S.9H 2 O was then introduced by syringe, giving a potential B 2 S content of 0.02 g.
Det resulterende olje/vandig væske/gass-systemet fikk likevektsinnstilles i 15 min., hvoretter i eksempler 2-5, rensemiddelet ble injisert i oppløsning i kolben, og den sistnevnte ble rystet. The resulting oil/aqueous liquid/gas system was allowed to equilibrate for 15 min., after which, in Examples 2-5, the cleaning agent was injected in solution into the flask, and the latter was shaken.
Etter ytterligere 15 min. ble en prøve av gassen fjernet til et "Gas-Tec"-detekteringsrør og hydrogensulfid-konsentrasjonen ble bestemt. Følgende resultater ble oppnådd: After another 15 min. a sample of the gas was removed to a "Gas-Tec" detection tube and the hydrogen sulphide concentration was determined. The following results were obtained:
Claims (8)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB868602319A GB8602319D0 (en) | 1986-01-30 | 1986-01-30 | Removing hydrogen sulphide from crude oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO870352D0 NO870352D0 (en) | 1987-01-28 |
| NO870352L true NO870352L (en) | 1987-07-31 |
Family
ID=10592245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO870352A NO870352L (en) | 1986-01-30 | 1987-01-28 | PROCEDURE FOR HYDROGEN SULFIDE REMOVAL. |
Country Status (2)
| Country | Link |
|---|---|
| GB (2) | GB8602319D0 (en) |
| NO (1) | NO870352L (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0411750B1 (en) * | 1989-06-06 | 1994-05-04 | Rohm And Haas Company | Organic stabilizers for isothiazolones |
-
1986
- 1986-01-30 GB GB868602319A patent/GB8602319D0/en active Pending
-
1987
- 1987-01-22 GB GB08701374A patent/GB2185995A/en not_active Withdrawn
- 1987-01-28 NO NO870352A patent/NO870352L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO870352D0 (en) | 1987-01-28 |
| GB2185995A (en) | 1987-08-05 |
| GB8602319D0 (en) | 1986-03-05 |
| GB8701374D0 (en) | 1987-02-25 |
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