NO177837B - Process for retarding formation of hydrate agglomerates - Google Patents
Process for retarding formation of hydrate agglomerates Download PDFInfo
- Publication number
- NO177837B NO177837B NO885789A NO885789A NO177837B NO 177837 B NO177837 B NO 177837B NO 885789 A NO885789 A NO 885789A NO 885789 A NO885789 A NO 885789A NO 177837 B NO177837 B NO 177837B
- Authority
- NO
- Norway
- Prior art keywords
- hydrates
- temperature
- acids
- fluid
- formation
- Prior art date
Links
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- 238000000034 method Methods 0.000 title claims description 17
- 230000000979 retarding effect Effects 0.000 title 1
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- 240000007817 Olea europaea Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
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- 229920002367 Polyisobutene Polymers 0.000 description 1
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- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
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- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/02—Pipe-line systems for gases or vapours
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
Oppfinnelsen angår en fremgangsmåte for å redusere tendensen til agglomerering av hydrater i et fluid som omfatter vann og en gass, under betingelser hvor hydrater kan dannes fra vannet og gassen. Spesielt vedrører oppfinnelsen en fremgangsmåte for å redusere dannelsen av og/eller redusere tendensen til å danne hydratagglomerater i naturgass, petroleumgass eller andre gasser ved anvendelse av minst én tilsetning. Gassene som danner hydrater kan spesielt omfatte f.eks. metan, etan, etylen, propan, propen, n-butan, i-butan, H2S og/eller C02. The invention relates to a method for reducing the tendency for hydrates to agglomerate in a fluid comprising water and a gas, under conditions where hydrates can be formed from the water and the gas. In particular, the invention relates to a method for reducing the formation of and/or reducing the tendency to form hydrate agglomerates in natural gas, petroleum gas or other gases by using at least one additive. The gases that form hydrates may in particular include e.g. methane, ethane, ethylene, propane, propene, n-butane, i-butane, H 2 S and/or CO 2 .
Disse hydratene dannes når vann er tilstede i nærvær av gass, enten i fri tilstand eller oppløst i en væskefase, såsom et flytende hydrokarbon, og når den temperaturen som nås av en blanding av spesielt vann, gass og eventuelt flytende hydrokarboner, såsom en olje, er lavere enn den termodynamiske dannelsestemperaturen for hydrater, idet denne temperaturen svarer til en kjent sammensetning av gasser under et bestemt trykk. These hydrates are formed when water is present in the presence of gas, either in the free state or dissolved in a liquid phase, such as a liquid hydrocarbon, and when the temperature reached by a mixture of particular water, gas and possibly liquid hydrocarbons, such as an oil, is lower than the thermodynamic formation temperature for hydrates, as this temperature corresponds to a known composition of gases under a certain pressure.
Dannelsen av hydrater er svært brysom, spesielt i olje-og gass-industrien, hvor betingelsene for dannelse av hydrater kan være tilstede. For å redusere kostnadene for produksjon av råolje og gass, i form av investerings- og driftskostnader i tilfelle offshore-produksjon spesielt, er en mulig løsning å redusere, eller endog å utelate de frem-gangsmåtene som anvendes på råoljen eller på gassen som skal transporteres fra feltet til kysten, og spesielt å etterlate noe eller alt vannet i det transporterte fluidet. Disse offshore-fremgangsmåtene blir vanligvis utført på en plattform plassert på overflaten nær et felt, på en slik måte at det opprinnelig varme utstrømmende mediet kan behandles før termodynamiske betingelser som er gunstige for dannelse av hydrater blir nådd, på grunn av avkjølingen av mediet med sjøvann. The formation of hydrates is very troublesome, especially in the oil and gas industry, where the conditions for the formation of hydrates may be present. In order to reduce the costs for the production of crude oil and gas, in the form of investment and operating costs in the case of offshore production in particular, a possible solution is to reduce, or even to omit, the procedures used on the crude oil or on the gas to be transported from the field to the coast, and in particular to leave some or all of the water in the transported fluid. These offshore processes are usually carried out on a platform located on the surface near a field, in such a way that the initially hot outflowing medium can be treated before thermodynamic conditions favorable for the formation of hydrates are reached, due to the cooling of the medium by seawater .
I praksis, når de termodynamiske betingelsene som kreves for dannelse av hydrater blir kombinert, fører agglomerer-ingen av hydratene imidlertid til oppfylling og blokkering av materørene ved å danne blokkeringer som hindrer all passasje av råolje eller gass. In practice, however, when the thermodynamic conditions required for the formation of hydrates are combined, the non-agglomeration of the hydrates leads to filling and blocking of the feed pipes by forming blockages that prevent all passage of crude oil or gas.
Dannelsen av hydratblokkeringer kan føre til stans i offshore-produksjonen og således innebære betydelige finan-sielle tap. Dessuten kan oppstartingen igjen av installa-sjonen, spesielt i tilfelle offshore-produksjon eller tran-sport, være en langvarig prosess, da det ikke er lett å ut-føre en dekomponering av de hydratene som er dannet. Når produksjonen fra et undervannsfelt med naturgass eller olje og gass som inneholder vann, når frem til overflaten av sjøbunnen og deretter blir transportert langs sjøbunnen, er de termodynamiske betingelsene i virkeligheten ofte tilstede for dannelse av hydrater, på grunn av en senkning av temperaturen på den produserte strømmen, og som da vil agglomerere og blokkere transportledningen. Temperaturen på sjøbunnen kem f.eks. være 3 eller 4°C. The formation of hydrate blockages can lead to a halt in offshore production and thus involve significant financial losses. Furthermore, restarting the installation, especially in the case of offshore production or transport, can be a lengthy process, as it is not easy to carry out a decomposition of the hydrates that have formed. When the production from an underwater field of natural gas or oil and gas containing water reaches the surface of the seabed and is then transported along the seabed, the thermodynamic conditions are in fact often present for the formation of hydrates, due to a lowering of the temperature of the produced the current, and which will then agglomerate and block the transport line. The temperature on the seabed will e.g. be 3 or 4°C.
Betingelser som favoriserer dannelsen av hydrater kan være tilstede på samme måten på land, i ledninger som ikke er nedgravet i det hele tatt, eller ikke er tilstrekkelig nedgravet i grunnnen, når f.eks. temperaturen på den omgivende luften er lav. Conditions favoring the formation of hydrates may be present in the same way on land, in conduits that are not buried at all, or not sufficiently buried in the ground, when e.g. the temperature of the surrounding air is low.
For å unngå disse ubehagelighetene går man enten til tilsetning av inhibitorer som reduserer den termodynamiske dannelsestemperaturen for hydratene, eller til å isolere rør-ledningene på en slik måte at man unngår at temperaturen på det transporterte fluidet kan nå temperaturen for hydrat-dannelse under de operasjonsbetingelsene som anvendes. To avoid these discomforts, one goes either to the addition of inhibitors that reduce the thermodynamic formation temperature for the hydrates, or to insulate the pipelines in such a way that one avoids that the temperature of the transported fluid can reach the temperature for hydrate formation under the operating conditions which is used.
Disse to løsningene er svært kostbare, da i det første tilfellet de mengder av dannelsesinhibitorer som tilsettes, hvorav de mest anvendte er metanol og etylenglykol, kan være opp til 10-20% av vanninnholdet, og disse inhibitorene er vanskelige å fjerne fullstendig. Når det gjelder den andre løsningen, er isolasjon av rørledningen også svært kostbar. These two solutions are very expensive, as in the first case the amounts of formation inhibitors that are added, of which the most used are methanol and ethylene glycol, can be up to 10-20% of the water content, and these inhibitors are difficult to remove completely. As for the second solution, insulation of the pipeline is also very expensive.
Det er blitt oppdaget at visse tilsetninger, som opptil nå ikke er blitt brukt for dette formålet, har stor virkning til å nedsette dannelsestemperaturen for hydratene og/eller å modifisere dannelsesmekanismen for disse hydratene fordi, istedenfor raskt å agglomerere til hverandre og danne faste blokkeringer, vil de dannede hydratene dispergeres i fluidet uten å agglomerere og tette igjen ledningene, så lenge som temperaturen på det transportere fluidet ikke er for lav. It has been discovered that certain additives, which until now have not been used for this purpose, have a great effect in lowering the formation temperature of the hydrates and/or in modifying the formation mechanism of these hydrates because, instead of quickly agglomerating to each other and forming solid blocks, the formed hydrates will be dispersed in the fluid without agglomerating and clogging the lines, as long as the temperature of the transporting fluid is not too low.
Anvendelse av disse tilsetningene er spesielt fordelaktig fra et økonomisk synspunkt, siden de mengdene som anvendes er svært lave (mindre enn 0,5 vektprosent i forhold til vann) og kostnadene for tilsetningene er moderate. The use of these additives is particularly advantageous from an economic point of view, since the quantities used are very low (less than 0.5% by weight in relation to water) and the costs of the additives are moderate.
Tilsetningene som anvendes ifølge oppfinnelsen, alene eller i kombinasjon eller kanskje i nærvær av andre forbindelser (metanol, glykol, overflateaktive stoffer) for å utsette dannelsen av og/eller redusere agglomereringstendensen for hydratene under slike betingelser at hydrater kan dannes, omfatter amfifile forbindelser, spesielt ikke-ioniske amfifile forbindelser eller amfifile forbindelser som omfatter minst én imidgruppe. The additives used according to the invention, alone or in combination or perhaps in the presence of other compounds (methanol, glycol, surfactants) to delay the formation of and/or reduce the agglomeration tendency of the hydrates under such conditions that hydrates can form, include amphiphilic compounds, in particular non-ionic amphiphilic compounds or amphiphilic compounds comprising at least one imide group.
Oppfinnelsen omfatter således en fremgangsmåte for å redusere tendensen til agglomerering av hydrater i et fluid som omfatter vann og en gass, under betingelser hvor hydrater kan dannes fra vann og nevnte gass, karakterisert ved at det i fluidet inkorporeres et additiv som omfatter minst én ikke-ionisk amfifil forbindelse, valgt fra The invention thus includes a method for reducing the tendency for hydrates to agglomerate in a fluid comprising water and a gas, under conditions where hydrates can be formed from water and said gas, characterized in that an additive comprising at least one non- ionic amphiphilic compound selected from
estere av polyoler, så som etylenglykol, polyalkylenglykoler, neopentylglykol, glycerol, polyglyceroler, trimetylolpropan, pentaerytritol, dipentaerytritol, sorbitol, sorbitan, mannitol, mannitan, glukose, sakkarose, esters of polyols, such as ethylene glycol, polyalkylene glycols, neopentyl glycol, glycerol, polyglycerols, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, mannitol, mannitan, glucose, sucrose,
fruktose og stivelse; med karboksylsyrer eller fructose and starch; with carboxylic acids or
-anhydrider valgt fra rettkjedede eller forgrenede, mettede eller umettede monokarboksylsyrer, hydroksykarboksylsyrer, epoksykarboksylsyrer, estoliserte syrer, dikarboksylsyrer eller -anhydrider, så som alkenylravsyre eller -anhydrid; eller dodekandikarboksylsyre, eller dimerer av fettsyrer, og trikarboksylsyrer, så som anhydrides selected from straight-chain or branched, saturated or unsaturated monocarboxylic acids, hydroxycarboxylic acids, epoxycarboxylic acids, estolized acids, dicarboxylic acids or anhydrides, such as alkenyl succinic acid or anhydride; or dodecanedicarboxylic acid, or dimers of fatty acids, and tricarboxylic acids, such as
trimerer fra fettsyrer, og trimers from fatty acids, and
forbindelser med imidfunksjon, så som alkenylsuksinimider. compounds with an imide function, such as alkenyl succinimides.
Ved amfifile forbindelser forstår man forbindelser som omfatter en hydrofil eller polar del og en oleofil eller lipofil del. Amphiphilic compounds are understood to mean compounds that comprise a hydrophilic or polar part and an oleophilic or lipophilic part.
Ikke-ioniske amfifile forbindelser karakteriseres ved å omfatte: en hydrofil del omfattende alkylenoksyd-, hydroksyl- eller alkylenamingrupper, Non-ionic amphiphilic compounds are characterized by comprising: a hydrophilic part comprising alkylene oxide, hydroxyl or alkylene amine groups,
- en oleofildel omfattende en hydrokarbonkjede avledet fra en alkohol, en fettsyre, et alkylert derivat av fenol - an oleophilic moiety comprising a hydrocarbon chain derived from an alcohol, a fatty acid, an alkylated derivative of phenol
eller et isobuten eller butenbasert polyolefin og or an isobutene or butene-based polyolefin and
- en binding mellom de hydrofile og oleofile delene som kan være f.eks. en eter-, ester- eller amidbro. Bindingen kan også skaffes ved et nitrogen- eller svovelatom. - a bond between the hydrophilic and oleophilic parts which can be e.g. an ether, ester or amide bridge. The bond can also be provided by a nitrogen or sulfur atom.
Blant de ikke-ioniske amfifile forbindelsene med en eter-bro kan nevnes oksyetylerte fettalkoholer, alkoksylerte alkylfenoler, oksyetylerte og/eller oksypropylerte derivater og sukkeretere. Among the non-ionic amphiphilic compounds with an ether bridge can be mentioned oxyethylated fatty alcohols, alkoxylated alkylphenols, oxyethylated and/or oxypropylated derivatives and sugar ethers.
De ikke-ioniske amfifile forbindelsene med en esterbro fremstilles ved kondensasjon av etylenoksyd og en fettsyre, eller fra estere av karboksylsyrer eller blandinger av karboksylsyrer eller fettsyrer på den ene siden, og alkoholer på den andre siden, eller fra karboksylsyre og alkohol-klorider, eller fra anhydrider og alkoholer. The non-ionic amphiphilic compounds with an ester bridge are prepared by condensation of ethylene oxide and a fatty acid, or from esters of carboxylic acids or mixtures of carboxylic acids or fatty acids on the one hand, and alcohols on the other hand, or from carboxylic acid and alcohol chlorides, or from anhydrides and alcohols.
Disse karboksylsyrene kan være lineære eller ikke-lineære karboksylsyrer (f.eks. forgrenet), mettede eller umettede, tilsvarende f.eks. fettsyrer som inneholdes i vegetabilsk og animalsk fett. Karboksylsyrene kan være alkoksylert. These carboxylic acids can be linear or non-linear carboxylic acids (e.g. branched), saturated or unsaturated, corresponding to e.g. fatty acids contained in vegetable and animal fats. The carboxylic acids can be carboxylated.
Blant de lineære mettede eller umettede syrene kan nevnes de følgende: smørsyre (C4:0), kapronsyre (C6:0), kaprylsyre (C8:0), kaprinsyre (C10:0), laurinsyre (C12:0), myristinsyre (C14:0), palmitinsyre (C16:0), stearinsyre (C18:0), arachidinsyre (C20:0), beheninsyre (C22:0), lignoserinsyre (C24:0), tilsvarende syrer med et like antall karbonatomer (4-24); de umettede syrene er: palmitoleinsyre (C16:l), elaidinsyre (C18:lt), oleinsyre (C18:lc), linolsyre (C18:2), linolensyre (C18:3), gadoleinsyre (C20:l), erusinsyre (C22:l). Antallet etyleniske umetninger er gitt for hver syre (0, 1, 2 elle-r 3); c betyr cis og t trans. Among the linear saturated or unsaturated acids, the following can be mentioned: butyric acid (C4:0), caproic acid (C6:0), caprylic acid (C8:0), capric acid (C10:0), lauric acid (C12:0), myristic acid (C14 :0), palmitic acid (C16:0), stearic acid (C18:0), arachidic acid (C20:0), behenic acid (C22:0), lignoseric acid (C24:0), corresponding acids with an equal number of carbon atoms (4-24 ); the unsaturated acids are: palmitoleic acid (C16:l), elaidic acid (C18:lt), oleic acid (C18:lc), linoleic acid (C18:2), linolenic acid (C18:3), gadoleic acid (C20:l), erucic acid (C22 :l). The number of ethylenic residues is given for each acid (0, 1, 2 or 3); c means cis and t trans.
Disse mettede og umettede syrene er vanligvis tilstede som sådanne eller i blanding i bundet form i oljer, estere og i fettsyreblandinger. These saturated and unsaturated acids are usually present as such or in admixture in bound form in oils, esters and in fatty acid mixtures.
De mest vanlige anvendte oljene er f.eks. jordnøtt, gammel og ny rapsfrø, kokosnøtt, bommulsfrø, hvetekim, mais, oliven, palme, palmenøtt, soyabønne, suet, talg, solsikke, smør, safflor, tallolje (harpiksekstrakt), fisk og karitt. The most common oils used are e.g. groundnut, old and new rapeseed, coconut, cottonseed, wheat germ, maize, olive, palm, palm nut, soybean, suet, tallow, sunflower, butter, safflower, tall oil (resin extract), fish and shea.
På lignende måte gir vegetabilske oljer eller animalsk fett mono- eller diglycerider som kan gi fordelaktige emulgerende egenskaper. Similarly, vegetable oils or animal fats provide mono- or diglycerides which can provide beneficial emulsifying properties.
Syrer med et ulik antall karbonatomer kan også anvendes. Acids with a different number of carbon atoms can also be used.
Karboksylsyrene kan være disyrer eller trisyrer tilsvarende dimere og trimere fettsyrer eller dikarboksylsyrer, såsom dodekandikarboksylsyre, hvori én av syregruppene kan være fri. The carboxylic acids can be diacids or triacids corresponding to dimer and trimeric fatty acids or dicarboxylic acids, such as dodecanedicarboxylic acid, in which one of the acid groups can be free.
Karboksylsyrene kan være ikke-lineære syrer, såsom abietinsyre. The carboxylic acids can be non-linear acids, such as abietic acid.
Karboksylsyren kan være undecyleninsyre. The carboxylic acid can be undecylenic acid.
Karboksylsyrene kan være hydroksykarboksylsyrer, såsom ricinoleinsyre eller hydroksystearinsyrer, avledet fra laksérolje eller hydrogenert ricinusolje. The carboxylic acids may be hydroxycarboxylic acids, such as ricinoleic acid or hydroxystearic acids, derived from castor oil or hydrogenated castor oil.
Karboksylsyrene kan være epoksykarboksylsyrer, såsom epoksystearinsyre eller blandinger avledet fra epoksyderte oljer. The carboxylic acids may be epoxy carboxylic acids, such as epoxy stearic acid or mixtures derived from epoxidized oils.
Karboksylsyrene kan være i form av polymerer, såsom estoliserte syrer som kan oppnås f.eks. fra ricinusolje og som har formelen: The carboxylic acids can be in the form of polymers, such as estolized acids which can be obtained e.g. from castor oil and which has the formula:
hvori 1 < x < 20 og n + m = 15. where 1 < x < 20 and n + m = 15.
Karboksylsyren kan være en alkenylravsyre, og anhydridet kan være et alkenylravsyreanhydrid. Alkenylgruppen i syren eller anhydridet kan avledes fra en polymer av et monoolefin som inneholder 2-5 karbonatomer. The carboxylic acid may be an alkenyl succinic acid, and the anhydride may be an alkenyl succinic anhydride. The alkenyl group in the acid or anhydride may be derived from a polymer of a monoolefin containing 2-5 carbon atoms.
Denne polymeren kan være en polyisobuten, hvori alkenylgruppen (f.eks. polyisobutenyl) har en gjennomsnittlig molekylvekt på fra 300-5000. This polymer may be a polyisobutene in which the alkenyl group (eg polyisobutenyl) has an average molecular weight of from 300-5000.
Alkoholene som anvendes kan være: The alcohols used can be:
monoalkoholer såsom laurylalkohol, monoalcohols such as lauryl alcohol,
dioler såsom etylenglykol, polyalkylenglykoler (såsom polyetylenglykol eller polypropylenglykol) eller neopentylglykol (NPG), diols such as ethylene glycol, polyalkylene glycols (such as polyethylene glycol or polypropylene glycol) or neopentyl glycol (NPG),
trioler, såsom glycerol eller trimetylolpropan (TNP), triols, such as glycerol or trimethylolpropane (TNP),
- tetroler, såsom pentaerytritol, erytritol (mono-, di-eller trisubstituert), sorbitol, polyoler såsom sorbitol, mannitol, polyglyceroler, dipentaerytritol eller sukkere såsom sakkarose, glukose, fruktose eller derivater av disse forskjellige produktene, såsom stivelse. - tetrols, such as pentaerythritol, erythritol (mono-, di- or tri-substituted), sorbitol, polyols such as sorbitol, mannitol, polyglycerols, dipentaerythritol or sugars such as sucrose, glucose, fructose or derivatives of these various products, such as starch.
Polyolestere som har frie hydroksylgrupper som muligens kan etoksyleres. Polyol esters that have free hydroxyl groups that can possibly be ethoxylated.
Polyglycerolene som anvendes kan være substituerte alkoksylerte polyglyceroler såsom mono- eller disubstituerte polyglyceroler. The polyglycerols used can be substituted alkoxylated polyglycerols such as mono- or disubstituted polyglycerols.
Tilsetningen kan omfatte elementer fra den følgende poly-glycerolestergruppen: triglycerolmono-oleat, heksaglycerol-mono-oleat, heksaglyceroltrioleat, decaglycerolmono-oleat, decaglycerolmonostearat, decaglycerolmonolaurat. • The additive may comprise elements from the following poly-glycerol ester group: triglycerol mono-oleate, hexaglycerol mono-oleate, hexaglycerol trioleate, decaglycerol mono-oleate, decaglycerol monostearate, decaglycerol monolaurate. •
I tillegg til de fordelaktige resultatene som polyglycerolene medfører mot dannelsen av hydrater og de blokkeringene som de frembringer, kan polyglycerolene ha svært forskjellig HLB (hydrofil-lipofil balanse), avhengig av graden av polymerisering, og kan således tilpasses optimalt til de forskjellige egenskapene hos fluidet som inneholder vann, gass og muligens en olje, såsom et kondensat. In addition to the beneficial results that the polyglycerols bring about against the formation of hydrates and the blockages that they produce, the polyglycerols can have very different HLB (hydrophilic-lipophilic balance), depending on the degree of polymerization, and can thus be optimally adapted to the different properties of the fluid containing water, gas and possibly an oil, such as a condensate.
Tilsetningene med amidbindinger som anvendes i oppfinnelsen skriver seg fra omsetningen mellom en karboksylsyre eller en metylester av en karboksylsyre og hydroksykarbyl-aminer, såsom dietanolamin eller monoetanolamin. The additions with amide bonds used in the invention result from the reaction between a carboxylic acid or a methyl ester of a carboxylic acid and hydroxycarbylamines, such as diethanolamine or monoethanolamine.
Bindingen mellom de hydrofile og lipofile delene av den tilsetningen som anvendes ifølge oppfinnelsen kan også skaffes ved et nitrogenatom, f.eks. ved kondensasjon av et fettamin med etylenoksyd, eller ved et svovelatom, f.eks. ved kondensasjon av etylenoksyd med merkaptaner. The bond between the hydrophilic and lipophilic parts of the additive used according to the invention can also be provided by a nitrogen atom, e.g. by condensation of a fatty amine with ethylene oxide, or by a sulfur atom, e.g. by condensation of ethylene oxide with mercaptans.
Tilsetningene som anvendes ifølge oppfinnelsen, omfattende minst én imidgruppe, kan fremstilles ved omsetning av et alkenylravsyreanhydrid med ett eller flere polyetylen-polyaminer på en slik måte at man oppnår alkenylsuksinimider. The additives used according to the invention, comprising at least one imide group, can be prepared by reacting an alkenyl succinic anhydride with one or more polyethylene polyamines in such a way that alkenyl succinimides are obtained.
Polyaminene som egner seg til fremstilling av slike alkenylsuksinimider tilsvarer mere spesielt den generelle formelen: The polyamines which are suitable for the preparation of such alkenyl succinimides correspond more particularly to the general formula:
hvori m er et helt tall fra 0 til 10. Disse biprimære polyaminene kan være f.eks. etylendiamin eller polyetylenpoly-aminer, såsom dietylentriamin, trietylentetramin, tetra-etylenpentamin, pentaetylenheksamin eller kommersielt til-gjengelige blandinger av disse polyaminene. in which m is an integer from 0 to 10. These biprimary polyamines can be e.g. ethylenediamine or polyethylene polyamines, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or commercially available mixtures of these polyamines.
Tilsetningen kan være i et forhold mellom 10 og 50.000 ppm i vekt i forhold til vann, og fortrinnsvis mellom 100 og 5000 ppm. The addition can be in a ratio between 10 and 50,000 ppm by weight in relation to water, and preferably between 100 and 5,000 ppm.
Dessuten kan tilsetningen koples med ett eller flere overflateaktive stoffer, fortrinnsvis anioniske overflateaktive stoffer, eller den kan bestå av en blanding av tilsetninger. Furthermore, the additive can be combined with one or more surfactants, preferably anionic surfactants, or it can consist of a mixture of additives.
Forbindelsene i blandingen kan ha den samme karboksylsyren og/eller polyolen felles. The compounds in the mixture may have the same carboxylic acid and/or polyol in common.
Dessuten kan tilsetningen omfatte en alkohol, såsom metanol, eller en polyalkoksyglykol. In addition, the additive may comprise an alcohol, such as methanol, or a polyalkyloxyglycol.
Nevnte tilsetning kan anvendes for å danne hydrater i dispergert tilstand og/eller for å transportere produsert råolje som inneholder vann og som danner hydrater med dette. Said addition can be used to form hydrates in a dispersed state and/or to transport produced crude oil which contains water and which forms hydrates with this.
Når nevnte tilsetning anvendes for å transportere den produserte råoljen, kan forbindelsen tilsettes til vannet og/eller til den produserte råoljen i et forhold mellom 50 og 50.000 ppm i vekt i forhold til vann, og fortrinnsvis i et forhold mellom 500 og 1000 ppm. When said addition is used to transport the produced crude oil, the compound can be added to the water and/or to the produced crude oil in a ratio between 50 and 50,000 ppm by weight in relation to water, and preferably in a ratio between 500 and 1000 ppm.
De følgende, eksemplene illustrerer oppfinnelsen uten på noen måte å begrense den. Eksemplene 1 og 2 er gitt som sammenligninger. The following examples illustrate the invention without limiting it in any way. Examples 1 and 2 are given as comparisons.
I disse eksemplene ble det utført tester på dannelsen av hydrater fra gass, kondensat og vann for å vurdere effektivi-teten av tilsetningene, ved å bruke det apparatet som er be-skrevet i det vedlagte diagrammet. In these examples, tests were carried out on the formation of hydrates from gas, condensate and water to assess the effectiveness of the additions, using the apparatus described in the attached diagram.
Apparatet består av en termoregulert reaktor 1 med et volum på 2 liter, hvori en væske 2, såsom en blanding av kondensat og vann, er plassert, og som omrøres kontinuerlig med en rører 3 forbundet med den ene enden av en turbin. Gassforsyningen til reaktor 1 reguleres med en trykkventil 4, temperaturen i reaktoren og sirkulasjonssløyfen kontrolleres med vannbad med konstant temperatur, hvor temperaturen reguleres med en temperaturregulator 5. Et rør 6 med den ene enden neddykket i væsken 1 forsyner med sin andre ende en sirkulasjonssløyfe 8 som kan lukkes ved ventilen 7. The apparatus consists of a thermoregulated reactor 1 with a volume of 2 litres, in which a liquid 2, such as a mixture of condensate and water, is placed, and which is stirred continuously with a stirrer 3 connected to one end of a turbine. The gas supply to reactor 1 is regulated with a pressure valve 4, the temperature in the reactor and the circulation loop is controlled with a constant temperature water bath, where the temperature is regulated with a temperature regulator 5. A pipe 6 with one end immersed in the liquid 1 supplies with its other end a circulation loop 8 which can be closed at valve 7.
Pumpen 9, som sørger for sirkulasjonen av fluidet og gassen, er forbundet med sirkulasjonssløyfen 8. Sløyfen 8 omfatter også et observasjonskammer 10, som kan isoleres ved to ventiler 11 og 12, hvori hydratdannelsen kan observeres. The pump 9, which ensures the circulation of the fluid and the gas, is connected to the circulation loop 8. The loop 8 also includes an observation chamber 10, which can be isolated by two valves 11 and 12, in which the hydrate formation can be observed.
Over og under dette kammeret finnes en trykkindikator 13 og en temperaturindikator 14. Apparatet omfatter en omkobling 15 forbi observasjonskammeret, og denne omkoblingen er ut-styrt med en beskyttelsesventil 16. Above and below this chamber there is a pressure indicator 13 and a temperature indicator 14. The apparatus includes a switch 15 past the observation chamber, and this switch is equipped with a protection valve 16.
Fluidet og gassen som har passert gjennom observasjonskammeret 10 eller omkoblingen 15 går tilbake til reaktoren via en tilbakeløpssløyfe 17. Ventilen 18 gjør det mulig å isolere tilbakeløpskretsen. Reaktoren 1 omfatter også en sikkerhetsventil 19. The fluid and gas that has passed through the observation chamber 10 or the switch 15 returns to the reactor via a return loop 17. The valve 18 makes it possible to isolate the return circuit. The reactor 1 also includes a safety valve 19.
Gassforsyningen til reaktoren 1 utføres med en krets be-tegnet 2 0 i sin helhet, og som omfatter følgende elementer i rekkefølge: et gassreservoar 21, en trykkreduksjonsventil 22, en fast trykkmåler 23 som kontrollerer trykkreduksjons-ventilen 22, en avstengningsventil 24, et filter 25, en kontrollventil 26, en strømningsmåler 27, en elektronisk ventil 28, kontrollert av trykkmåleren 4, og som sørger for et bestemt trykk i reaktoren ved forandring av gasstrømmen, en beskyttelsesventil 29 og en forsyningssløyfe 30 som går til reaktoren. The gas supply to the reactor 1 is carried out with a circuit designated 20 in its entirety, and which comprises the following elements in order: a gas reservoir 21, a pressure reduction valve 22, a fixed pressure gauge 23 which controls the pressure reduction valve 22, a shut-off valve 24, a filter 25, a control valve 26, a flow meter 27, an electronic valve 28, controlled by the pressure gauge 4, and which ensures a certain pressure in the reactor by changing the gas flow, a protection valve 29 and a supply loop 30 that goes to the reactor.
I et praktisk eksempel har sirkulasjonssløyfen 8 en lengde på 10 meter og er i form av en rørledning med en indre diameter på omlag 19 mm (3/4") . Sirkulasjonspumpen 9 tillater strømningshastigheter opptil 1 m/s. In a practical example, the circulation loop 8 has a length of 10 meters and is in the form of a pipeline with an internal diameter of approximately 19 mm (3/4"). The circulation pump 9 allows flow rates up to 1 m/s.
Dannelsen av hydrater ved reaksjon mellom gass og vann kan observeres ved gassforbruket som bestemmes ved strømningsmåleren 27 og som kontrolleres ved den elektroniske ventilen 28 og differensialtrykkmåleren 23, på en slik måte at trykket holdes konstant i kretsen innenfor pluss eller minus 1/50 av en bar. The formation of hydrates by reaction between gas and water can be observed by the gas consumption which is determined by the flow meter 27 and which is controlled by the electronic valve 28 and the differential pressure meter 23, in such a way that the pressure is kept constant in the circuit within plus or minus 1/50 of a bar .
For å bestemme temperaturen hvorved hydratene dannes, får man istand en rask senkning av temperaturen på 3°C pr. time fra omgivende temperatur til 1°C. To determine the temperature at which the hydrates are formed, a rapid lowering of the temperature of 3°C per hour from ambient temperature to 1°C.
Når man har notert den temperaturen hvorved hydratene dannes, observert ved hjelp av gassforbruket, øker man temperaturen i reaktoren og sirkulasjonssløyfen til 5°C over denne dannelsestemperaturen og venter inntil dekomponeringen av hydratene er fullstendig. Denne dekomponeringen viser seg ved en økning av trykket i reaktoren 1 og ved at opasiteten av fluidet, som frembringes ved nærværet av hydrater, for-svinner visuelt. Once the temperature at which the hydrates are formed, observed by means of the gas consumption, has been noted, the temperature in the reactor and the circulation loop is increased to 5°C above this formation temperature and wait until the decomposition of the hydrates is complete. This decomposition is manifested by an increase in the pressure in the reactor 1 and by the fact that the opacity of the fluid, which is produced by the presence of hydrates, disappears visually.
Til slutt frembringer man en langsom økning av temperaturen, av størrelsesorden l°C/time, og den temperaturen hvorved hydratene begynner å danne seg bestemmes, og deretter bestemmes den temperaturen hvorved kretsen er fullstendig blokkert og ingen sirkulasjon av fluidet er mulig. Finally, a slow increase in temperature is produced, of the order of 1°C/hour, and the temperature at which the hydrates begin to form is determined, and then the temperature at which the circuit is completely blocked and no circulation of the fluid is possible is determined.
Eksempel nr. 1 Example No. 1
I dette eksempelet arbeider man med et fluid som består av 20 volumprosent vann og 80 volumprosent kondensat. Den vektmessige sammensetningen av kondensatet er: for molekyler som har mindre enn 11 karbonatomer: 20% paraffiner og isoparaffiner, 48% naftener, 10% aromater; og for molekyler som har minst 11 karbonatomer: 22% av en blanding av paraffiner, isoparaffiner, naftener og aromater. Gassen som anvendes omfatter 98 volumprosent metan og 2 volumprosent etan. Eksperi-mentene utføres under et trykk på 7 MPa, som holdes konstant ved forsyning av gass. In this example, you are working with a fluid that consists of 20 volume percent water and 80 volume percent condensate. The composition by weight of the condensate is: for molecules having less than 11 carbon atoms: 20% paraffins and isoparaffins, 48% naphthenes, 10% aromatics; and for molecules having at least 11 carbon atoms: 22% of a mixture of paraffins, isoparaffins, naphthenes and aromatics. The gas used comprises 98 volume percent methane and 2 volume percent ethane. The experiments are carried out under a pressure of 7 MPa, which is kept constant by supplying gas.
Under disse betingelsene er den temperaturen, hvorved hydratene begynner å danne seg, under den andre temperatur-økningen, 11,4°C og blokkering av sirkulasjonen ved økning og koalescering av hydratene finner sted når temperaturen når +11°C (284 K), dvs. 24 minutter etter at hydratene begynner å danne seg. Under these conditions, the temperature at which the hydrates start to form, during the second temperature increase, is 11.4°C and blocking of the circulation by increase and coalescence of the hydrates takes place when the temperature reaches +11°C (284 K), i.e. 24 minutes after the hydrates start to form.
Eksempel nr. 2 Example No. 2
I dette eksempelet går man frem som i eksempel nr. 1 med det samme fluidet, den samme gassen og det samme trykket, men man tilsetter til det sirkulerende fluidet 5 vektprosent metanol i forhold til vannet i blandingen. Under disse betingelsene observerer man at den temperaturen, hvorved hydratene begynner å danne seg, er 9,4°C og at den temperaturen hvorved ingen sirkulasjon av fluidet er mulig, er 9°C. In this example, one proceeds as in example no. 1 with the same fluid, the same gas and the same pressure, but one adds to the circulating fluid 5 percent by weight of methanol in relation to the water in the mixture. Under these conditions, it is observed that the temperature at which the hydrates begin to form is 9.4°C and that the temperature at which no circulation of the fluid is possible is 9°C.
Eksempel nr. 3 Example No. 3
Man går frem som i eksempel nr. 1, men tilsetter til det sirkulerende fluidet 0,2 vektprosent sorbitanmonolaurat i forhold til vann. Proceed as in example no. 1, but add to the circulating fluid 0.2% by weight of sorbitan monolaurate in relation to water.
Under disse betingelsene observerer man at den temperaturen, hvorved hydratene begynner å danne seg, er 9,7°C og at blokkeringen av fluidsirkulasjonen finner sted ved +5°C. Under these conditions, it is observed that the temperature at which the hydrates begin to form is 9.7°C and that the blockage of the fluid circulation takes place at +5°C.
Eksempel nr. 4 Example No. 4
Man går frem som i eksempel nr. 1, men tilsetter til det sirkulerende fluidet 0,2 vektprosent i forhold til vann av en blanding av 80 vektprosent sorbitanmonolaurat og 20 vektprosent natriumdioktylsulfosuccinat (ved en konsentrasjon på 65 vektprosent). One proceeds as in example no. 1, but adds to the circulating fluid 0.2 percent by weight in relation to water of a mixture of 80 percent by weight sorbitan monolaurate and 20 percent by weight sodium dioctyl sulfosuccinate (at a concentration of 65 percent by weight).
Under disse betingelsene observerer man at den temperaturen, hvorved hydratene begynner å danne seg, er 9,3°C og at blokkeringen av fluidsirkulasjonen finner sted ved +4,5°C. Under these conditions, it is observed that the temperature at which the hydrates begin to form is 9.3°C and that the blockage of the fluid circulation takes place at +4.5°C.
Eksempel nr. 5 Example No. 5
Man går frem som i eksempel nr. 5, men tilsetter til det sirkulerende fluidet 0,2 vektprosent i forhold til vann, av en blanding bestående av 50 vektprosent sorbitanmonolaurat og 50 vektprosent sorbitantrioleat. One proceeds as in example no. 5, but adds to the circulating fluid 0.2 percent by weight in relation to water, of a mixture consisting of 50 percent by weight sorbitan monolaurate and 50 percent by weight sorbitan trioleate.
Under disse betingelsene observerer man at den temperaturen , hvorved hydratene begynner å danne seg, er 9,2 ° C og at blokkeringen av fluidsirkulasjonen finner sted ved +2°C. Under these conditions, it is observed that the temperature at which the hydrates begin to form is 9.2°C and that the blocking of the fluid circulation takes place at +2°C.
Eksempel nr. 6 Example No. 6
Man går frem som i eksempel nr. 1, men tilsetter tii det sirkulerende fluidet 0,2 vektprosent i forhold til vann, av etoksylert sorbitanmonolaurat som har et etoksyleringsforhold på 20. One proceeds as in example no. 1, but adds to the circulating fluid 0.2 percent by weight in relation to water, of ethoxylated sorbitan monolaurate which has an ethoxylation ratio of 20.
Under disse betingelsene observerer man at den temperaturen, hvorved hydratene begynner å danne seg, er 9,3°C og at blokkeringen av fluidsirkulasjonen finner sted ved +3°C. Under these conditions, it is observed that the temperature at which the hydrates begin to form is 9.3°C and that the blockage of the fluid circulation takes place at +3°C.
Eksempel nr. 7 Example No. 7
Man går frem som i eksempel nr. 1, men tilsetter til det sirkulerende fluidet 0,2 vektprosent i forhold til vann, av en blanding av 50 vektprosent etoksylert sorbitanmonolaurat med et etoksyleringsforhold på 20, og 50 vektprosent sorbitansesquioleat. One proceeds as in example no. 1, but adds to the circulating fluid 0.2 percent by weight in relation to water, of a mixture of 50 percent by weight ethoxylated sorbitan monolaurate with an ethoxylation ratio of 20, and 50 percent by weight sorbitan sesquioleate.
Under disse betingelsene observerer man at den temperaturen, hvorved hydratene begynner å danne seg, er 8,8°C og at blokkeringen av fluidsirkulasjonen finner sted ved -3"C.'Under these conditions, it is observed that the temperature at which the hydrates begin to form is 8.8°C and that the blockage of fluid circulation takes place at -3°C.
Eksempel nr. 8 Example No. 8
Man går frem som i eksempel nr. 1, men tilsetter til det sirkulerende fluidet 0,5 vektprosent i forhold til vann, av en løsning som inneholder 70 vektprosent polyisobutenyl-suksinimid i en aromatisk fraksjon. Polyisobutenylsuksin-imidet fremstilles ved omsetning av polyisobutenylravsyre-anhydrid (hvis polyisobutenylgruppe har en midlere molekylvekt på omlag 3000) og en kommersiell blanding av tetra-etylenpentamin (TEPA), i et molforhold anhydrid/TEPA på 1,5. One proceeds as in example no. 1, but adds to the circulating fluid 0.5 percent by weight in relation to water, of a solution containing 70 percent by weight of polyisobutenyl succinimide in an aromatic fraction. The polyisobutenyl succinimide is produced by reacting polyisobutenyl succinic anhydride (whose polyisobutenyl group has an average molecular weight of around 3000) and a commercial mixture of tetraethylenepentamine (TEPA), in a molar ratio anhydride/TEPA of 1.5.
Under disse betingelsene observerer man at den temperaturen, hvorved hydratene begynner å danne seg, er 7,4°C og at blokkeringen av fluidsirkulasjonen finner sted ved +2°C. Under these conditions, it is observed that the temperature at which the hydrates begin to form is 7.4°C and that the blockage of the fluid circulation takes place at +2°C.
Eksempel nr. 9 Example No. 9
Man går frem som i eksempel nr. 1, men tilsetter til det sirkulerende fluidet 0,2 vektprosent i forhold til vann, av en blanding av 50 vektprosent etoksylert nonylfenol med en tetthet lik 1,12 og 50 vektprosent oktylfenol med tetthet lik 1,075. One proceeds as in example no. 1, but adds to the circulating fluid 0.2 percent by weight in relation to water, of a mixture of 50 percent by weight ethoxylated nonylphenol with a density equal to 1.12 and 50 percent by weight octylphenol with a density equal to 1.075.
Under disse betingelsene observerer man at den temperaturen, hvorved hydratene begynner å danne seg, er 10,2°C og at blokkeringen av fluidsirkulasjonen finner sted ved +7,2°C. Under these conditions, it is observed that the temperature at which the hydrates begin to form is 10.2°C and that the blockage of the fluid circulation takes place at +7.2°C.
Eksempel nr. 10 Example No. 10
Man går frem som i eksempel nr. 1, men tilsetter til det sirkulerende fluidet 0,5 vektprosent i forhold til vann, av palmitinsyremonoglycerid. One proceeds as in example no. 1, but adds to the circulating fluid 0.5 percent by weight in relation to water, of palmitic acid monoglyceride.
Under disse betingelsene observerer man at den temperaturen, hvorved hydratene begynner å danne seg, er 7,9°C og at blokkeringen av fluidsirkulasjonen finner sted ved +5,6°C. Under these conditions, it is observed that the temperature at which the hydrates begin to form is 7.9°C and that the blockage of the fluid circulation takes place at +5.6°C.
Eksempel nr. 11 Example No. 11
Man går frem som i eksempel nr. 1, men tilsetter til det sirkulerende fluidet 0,5 vektprosent i forhold til vann av en blanding av 85 vektprosent palmitinsyremonoglycerid og 15 vektprosent natriumdioktylsulfosuksinat (ved en konsentrasjon på 65 vektprosent). One proceeds as in example no. 1, but adds to the circulating fluid 0.5 percent by weight in relation to water of a mixture of 85 percent by weight palmitic acid monoglyceride and 15 percent by weight sodium dioctyl sulfosuccinate (at a concentration of 65 percent by weight).
Under disse betingelsene observerer man at den temperaturen, hvorved hydratene begynner å danne seg, er 7,8°C og at blokkeringen av fluidsirkulasjonen finner sted ved +5,1°C. Under these conditions, it is observed that the temperature at which the hydrates begin to form is 7.8°C and that the blockage of the fluid circulation takes place at +5.1°C.
Eksempel nr. 12 Example No. 12
Man går frem som i eksempel nr. 1, men tilsetter til det sirkulerende fluidet 0,4 vektprosent (i forhold til vann), av en løsning som inneholder 50 vektprosent polyetylenglykol-polyisobutenylsuksinat i en aromatisk hydrokarbonfraksjon i form av en vanlig handelsvare. One proceeds as in example no. 1, but adds to the circulating fluid 0.4 percent by weight (in relation to water) of a solution containing 50 percent by weight polyethylene glycol-polyisobutenyl succinate in an aromatic hydrocarbon fraction in the form of a common commercial product.
Polyetylenglykol-polyisobutenylsuksinatet ble oppnådd ved å reagere et polyisobutenyl-ravsyrenanhydrid hvor polyisobu-tenylgruppen har en antallsmidlere molekylvekt nær 1000 og en polyetylenglykol med en molekylvekt nær 400, i et molforhold på 1. The polyethylene glycol-polyisobutenyl succinate was obtained by reacting a polyisobutenyl-succinic nanhydride where the polyisobutenyl group has a number-average molecular weight close to 1000 and a polyethylene glycol with a molecular weight close to 400, in a molar ratio of 1.
Under disse betingelsene observeres det at hydratene begynner å danne seg ved 7,5°C og at blokkeringen av fluidsirkulasjonen finner sted ved -2°C. Under these conditions, it is observed that the hydrates start to form at 7.5°C and that the blockage of the fluid circulation takes place at -2°C.
Det kan sees at polyetylenglykol-polyisobutenylsuksinatet er virksomt i henhold til oppfinnelsen når det gjelder å senke temperaturen hvor hydrater agglomererer, slik at agglomereringstendensen således reduseres. It can be seen that the polyethylene glycol-polyisobutenyl succinate is effective according to the invention when it comes to lowering the temperature at which hydrates agglomerate, so that the agglomeration tendency is thus reduced.
I eksemplene 1 og 2, i nærvær av bare metanol eller med bare det fluidet som skal testes, observerer man at In examples 1 and 2, in the presence of only methanol or with only the fluid to be tested, it is observed that
Claims (10)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8718433A FR2625547B1 (en) | 1987-12-30 | 1987-12-30 | PROCESS FOR DELAYING FORMATION AND / OR REDUCING THE TENDENCY TO AGGLOMERATION OF HYDRATES |
Publications (4)
Publication Number | Publication Date |
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NO885789D0 NO885789D0 (en) | 1988-12-28 |
NO885789L NO885789L (en) | 1989-07-03 |
NO177837B true NO177837B (en) | 1995-08-21 |
NO177837C NO177837C (en) | 1995-11-29 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO885789A NO177837C (en) | 1987-12-30 | 1988-12-28 | Process for retarding formation of hydrate agglomerates |
Country Status (6)
Country | Link |
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EP (1) | EP0323774B1 (en) |
JP (1) | JPH023497A (en) |
BR (1) | BR8806978A (en) |
CA (1) | CA1337017C (en) |
FR (1) | FR2625547B1 (en) |
NO (1) | NO177837C (en) |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
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GB9115095D0 (en) * | 1991-07-12 | 1991-08-28 | Shell Int Research | A method for preventing or retarding the formation of hydrates |
FR2694213B1 (en) * | 1992-08-03 | 1994-10-14 | Inst Francais Du Petrole | Method for reducing the tendency to agglomerate hydrates in production effluents. |
FR2697264B1 (en) * | 1992-10-23 | 1994-12-30 | Inst Francais Du Petrole | Method for reducing the tendency for hydrates to agglomerate in production effluents. |
US5432292A (en) * | 1992-11-20 | 1995-07-11 | Colorado School Of Mines | Method for controlling clathrate hydrates in fluid systems |
WO1994025727A1 (en) * | 1993-05-04 | 1994-11-10 | Bp Exploration Operating Company Limited | Hydrate inhibition |
FR2733512B1 (en) * | 1995-04-26 | 1997-07-04 | Inst Francais Du Petrole | PROCESS FOR INHIBITING OR DELAYING THE FORMATION, GROWTH AND / OR AGGLOMERATION OF HYDRATES IN PRODUCTION EFFLUENTS |
CO4560488A1 (en) * | 1995-10-03 | 1998-02-10 | Nor Ind Inc | CLEANING COMPOSITIONS FOR LINE WELLS, HOUSINGS, TRAININGS AND OIL AND GAS EQUIPMENT. |
JP3018976B2 (en) * | 1995-12-28 | 2000-03-13 | 富士ゼロックス株式会社 | Semiconductor light receiving element |
FR2748773B1 (en) * | 1996-05-15 | 1998-06-26 | Inst Francais Du Petrole | PROCESS FOR INHIBITING OR DELAYING THE FORMATION OR AGGLOMERATION OF HYDRATES IN A PRODUCTION EFFLUENT |
DE19642656A1 (en) * | 1996-10-16 | 1998-04-23 | Bayer Ag | Method of preventing gas hydrates |
FR2767068B1 (en) * | 1997-08-05 | 1999-09-17 | Inst Francais Du Petrole | PROCESS FOR DELAYING GROWTH AND / OR AGGLOMERATION OF HYDRATES IN A PRODUCTION EFFLUENT |
EP0896123B1 (en) * | 1997-08-05 | 2005-07-27 | Institut Français du Pétrole | Process to slow down the growth and/or the agglomeration and possibly delaying the formation of hydrates in a production effluent |
FR2767067B1 (en) * | 1997-08-05 | 1999-09-17 | Inst Francais Du Petrole | PROCESS FOR INHIBITING FORMATION AND DELAYING GROWTH AND / OR AGGLOMERATION OF HYDRATES IN A PRODUCTION EFFLUENT |
FR2771445B1 (en) * | 1997-11-25 | 1999-12-31 | Inst Francais Du Petrole | PROCESS FOR DELAYING GROWTH AND / OR AGGLOMERATION OF HYDRATES IN A PRODUCTION EFFLUENT |
FR2792997B1 (en) | 1999-04-29 | 2001-06-29 | Inst Francais Du Petrole | FORMULATION OF ADDITIVES FOR IMPROVING THE TRANSPORT OF PETROLEUM EFFLUENTS LIKELY TO CONTAIN HYDRATES AND METHOD USING THIS FORMULATION |
US6359047B1 (en) | 2001-03-20 | 2002-03-19 | Isp Investments Inc. | Gas hydrate inhibitor |
DE10147650A1 (en) * | 2001-09-27 | 2003-04-10 | Basf Ag | Hydrophilic emulsifiers based on polyisobutylene |
FR2851284A1 (en) * | 2003-02-19 | 2004-08-20 | Inst Francais Du Petrole | METHOD FOR AVOIDING SEDIMENTATION OF GAS HYDRATE CRYSTALS |
FR2879189B1 (en) * | 2004-12-13 | 2007-03-30 | Inst Francais Du Petrole | METHOD FOR TRANSPORTING SUSPENDED HYDRATES INTO PRODUCTION EFFLUENTS USING A NON-POLLUTANT ADDITIVE |
DE102005006421A1 (en) | 2005-02-12 | 2006-08-24 | Clariant Produkte (Deutschland) Gmbh | Polymers and their preparation and use as gas hydrate inhibitors |
DE102005007287B4 (en) * | 2005-02-17 | 2007-01-25 | Clariant Produkte (Deutschland) Gmbh | Use of polyesters as gas hydrate inhibitors |
FR2914565B1 (en) * | 2007-04-05 | 2009-05-22 | Inst Francais Du Petrole | PROCESS FOR ENRICHING ACIDIC GASES WITH GASEOUS EFFLUENT |
JP5489150B2 (en) * | 2009-02-26 | 2014-05-14 | 学校法人日本大学 | Production method of clathrate hydrate |
US9145465B2 (en) | 2011-10-20 | 2015-09-29 | Baker Hughes Incorporated | Low dosage kinetic hydrate inhibitors for natural gas production systems |
CN103438353B (en) * | 2013-06-27 | 2015-11-18 | 北京航天发射技术研究所 | A kind of redundancy is for air circuit |
BR112021007666A2 (en) * | 2018-10-29 | 2021-07-27 | Championx Usa Inc. | method for inhibiting the formation of agglomerates of natural gas hydrates, composition, and use of the succinimide-based compound. |
Family Cites Families (4)
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FR1133416A (en) * | 1954-05-10 | 1957-03-27 | Stanolind Oil & Gas Co | Improvements to a process for increasing the efficiency of an oil well |
US2865453A (en) * | 1956-10-09 | 1958-12-23 | Texas Co | Well treatment to remove a water block |
US3644107A (en) * | 1970-03-09 | 1972-02-22 | Phillips Petroleum Co | Method for preventing the formation of hydrates and ice |
FR2570162B1 (en) * | 1984-09-07 | 1988-04-08 | Inst Francais Du Petrole | METHOD AND DEVICE FOR COMPRESSING AND TRANSPORTING A GAS CONTAINING A LIQUID FRACTION |
-
1987
- 1987-12-30 FR FR8718433A patent/FR2625547B1/en not_active Expired - Lifetime
-
1988
- 1988-12-16 EP EP19880403203 patent/EP0323774B1/en not_active Expired - Lifetime
- 1988-12-27 JP JP33076488A patent/JPH023497A/en active Pending
- 1988-12-28 NO NO885789A patent/NO177837C/en unknown
- 1988-12-29 BR BR8806978A patent/BR8806978A/en not_active IP Right Cessation
- 1988-12-30 CA CA 587342 patent/CA1337017C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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EP0323774B1 (en) | 1993-05-05 |
JPH023497A (en) | 1990-01-09 |
FR2625547B1 (en) | 1990-06-22 |
NO177837C (en) | 1995-11-29 |
EP0323774A1 (en) | 1989-07-12 |
NO885789D0 (en) | 1988-12-28 |
CA1337017C (en) | 1995-09-19 |
NO885789L (en) | 1989-07-03 |
BR8806978A (en) | 1989-09-05 |
FR2625547A1 (en) | 1989-07-07 |
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