NO823593L - PROCEDURE FOR SEPARATING OIL OIL EMULSES OF THE WATER-I OIL TYPE. - Google Patents
PROCEDURE FOR SEPARATING OIL OIL EMULSES OF THE WATER-I OIL TYPE.Info
- Publication number
- NO823593L NO823593L NO823593A NO823593A NO823593L NO 823593 L NO823593 L NO 823593L NO 823593 A NO823593 A NO 823593A NO 823593 A NO823593 A NO 823593A NO 823593 L NO823593 L NO 823593L
- Authority
- NO
- Norway
- Prior art keywords
- weight
- ethylene oxide
- block polymer
- oil
- propylene oxide
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 11
- 229920000642 polymer Polymers 0.000 claims description 40
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 34
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- -1 polyoxypropylene core Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- QLCJOAMJPCOIDI-UHFFFAOYSA-N 1-(butoxymethoxy)butane Chemical compound CCCCOCOCCCC QLCJOAMJPCOIDI-UHFFFAOYSA-N 0.000 description 1
- IRTCJFCIQKNFPP-UHFFFAOYSA-N 2-methyl-1,4-dioxane Chemical compound CC1COCCO1 IRTCJFCIQKNFPP-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- UXHQLGLGLZKHTC-CUNXSJBXSA-N 4-[(3s,3ar)-3-cyclopentyl-7-(4-hydroxypiperidine-1-carbonyl)-3,3a,4,5-tetrahydropyrazolo[3,4-f]quinolin-2-yl]-2-chlorobenzonitrile Chemical compound C1CC(O)CCN1C(=O)C1=CC=C(C=2[C@@H]([C@H](C3CCCC3)N(N=2)C=2C=C(Cl)C(C#N)=CC=2)CC2)C2=N1 UXHQLGLGLZKHTC-CUNXSJBXSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical class OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G4/00—Condensation polymers of aldehydes or ketones with polyalcohols; Addition polymers of heterocyclic oxygen compounds containing in the ring at least once the grouping —O—C—O—
-
- 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
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Removal Of Floating Material (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Polyethers (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
Oppfinnelsen vedrører en fremgangsmåte til adskillelse av jordoljeemulsjoner av typen vann-i-olje ved tilsetning av forbindelser fra gruppen av ved hjelp av koblingsmidler forbundede etylenoksyd-propylenoksyd-blokkpolymerisater. The invention relates to a method for separating petroleum emulsions of the water-in-oil type by adding compounds from the group of ethylene oxide-propylene oxide block polymers connected by means of coupling agents.
I US-patent nr. 2 674 619 og i tysk patent nr. 1 018 179 er In US patent no. 2,674,619 and in German patent no. 1,018,179,
det omtalt blokkpolymerisater av etylenoksyd og propylenoksyd. De består av en polyoksypropylenkjerne med en gjennomsnittlig molekylvekt på minst 900 og to ved dets to ender tilsluttede polyoksyetylengrupper med (til sammen) minst 10 vekt-% etylenoksyd, referert til vekten av blokkpolymerisatet. Fra den nevnte tyske patent er det videre kjent at disse blokkpolymerisater er virksomme jordoljespaltere, da det med deres hjelp oppnås en relativt hurtig adskillelse av jordoljeemulsjoner av vann-i-olje typen. the mentioned block polymers of ethylene oxide and propylene oxide. They consist of a polyoxypropylene core with an average molecular weight of at least 900 and two polyoxyethylene groups attached at its two ends with (in total) at least 10% by weight of ethylene oxide, referred to the weight of the block polymer. From the aforementioned German patent it is further known that these block polymers are effective petroleum splitters, as with their help a relatively rapid separation of petroleum emulsions of the water-in-oil type is achieved.
I tysk Offenlegungsskrift nr. 1 495 827 og i britisk patent In German Offenlegungsskrift No. 1 495 827 and in British Patent
nr. 1 112 908 er det omtalt anvendelsen av med diisocyanter som koblingsmiddel forbundede etylenoksyd-propylenoksyd-blokkpolymerisater til spalting av råoljeemulsjoner. Disse, koblede etylenoksyd-propylenoksyd-blokkpolymere fåes ved omsetning av de i US-patent nr. 2 674 619 og tysk patent nr. no. 1 112 908, the use of ethylene oxide-propylene oxide block polymers connected with diisocyanates as a coupling agent for splitting crude oil emulsions is discussed. These linked ethylene oxide-propylene oxide block polymers are obtained by converting those in US patent no. 2,674,619 and German patent no.
1 018 179 omtalte etylenoksy-propylenoksyd-blokkpolymere 1,018,179 disclosed ethyleneoxy-propylene oxide block polymers
med alifatiske eller aromatiske diisocyanter. with aliphatic or aromatic diisocyanates.
En annen type av koblede etylenoksyd-propylenoksyd-blokkpolymerisater er omtalt i tysk Offenlegungsskrift nr. 25 36 121 og i US-patent nr. 4 189 609. De fåes ved at etylenoksyd- og propylenoksyd-blokkpolymerisater omsettes med formaldehyd eller dialkylkarbonater som koblingsstoffer i nærvær av sure resp. alkaliske katalysatorer. Ifølge de to publikasjoner er de således dannede produkter på grunn av deres spesielle kjemiske struktur lett hydrolyserbare og egner seg til anvendelse som skumundertrykningsmidler, Another type of linked ethylene oxide-propylene oxide block polymers is described in German Offenlegungsskrift no. 25 36 121 and in US patent no. 4 189 609. They are obtained by reacting ethylene oxide and propylene oxide block polymers with formaldehyde or dialkyl carbonates as coupling agents in the presence of sour resp. alkaline catalysts. According to the two publications, the products thus formed are, due to their special chemical structure, easily hydrolyzable and suitable for use as foam suppressants,
som fuktemidler ved papirfremstilling og som glidemiddel i tekstilindustrien. Muligheten for en anvendelse som emul-sjonsspaltere, spesielt som spaltere av jordoljeemulsjoner as wetting agents in paper production and as a lubricant in the textile industry. The possibility of an application as emulsion splitters, especially as splitters of petroleum emulsions
av vann-i-olje typen, nevnes eller antydes ikke i de to publikasjoner. of the water-in-oil type, is not mentioned or implied in the two publications.
Det er nå overraskende funnet at koblede etylenoksyd-propylenoksyd-blokkpolymerisater av den i US-patent nr. 4 189 609 It has now surprisingly been found that linked ethylene oxide-propylene oxide block polymers of that in US Patent No. 4,189,609
og i tysk Offenlegungsskrift nr. 25 36 121 omtalte type er spesielt virksomme oljespaltere. and the type mentioned in German Offenlegungsskrift No. 25 36 121 are particularly effective oil splitters.
Følgelig er fremgangsmåten ifølge oppfinnelsen til adskillelse av jordoljeemulsjoner av typen vann-i-olje ved tilsetning av forbindelser fra gruppen av de ved hjelp av koblingsmidlet forbundede etylenoksyd-propylenoksyd-blokkpolymerisaterkarakterisert vedat det til jordoljeemulsjonene settes en mengde på minst 5 ppm, forbindelser som er blitt dannet ved omsetning av Consequently, the method according to the invention for separating petroleum emulsions of the water-in-oil type by adding compounds from the group of ethylene oxide-propylene oxide block polymers connected by means of the coupling agent is characterized by adding to the petroleum emulsions an amount of at least 5 ppm, compounds which have been formed by turnover of
a) et blokkpolymerisat av propylenoksyd og etylenoksyd med en gjennomsnittlig molekylvekt fra 1650-7000 og med a) a block polymer of propylene oxide and ethylene oxide with an average molecular weight from 1650-7000 and with
10-50 vekt-% etylenoksyd-enheter og 50-90 vekt-% propylenoksyd-enheter, referert til blokkpolymerisatet med b) formaldehyd i en 0,5 til to ganger støkiometrisk mengde, referert til mengden av OH-grupper i det anvendte blokk--polymerisat, i nærvær av sure katalysatorer og ved en temperatur fra 50-180°C. 10-50% by weight ethylene oxide units and 50-90% by weight propylene oxide units, referred to the block polymer with b) formaldehyde in a 0.5 to twice stoichiometric amount, referred to the amount of OH groups in the block used -polymer, in the presence of acid catalysts and at a temperature from 50-180°C.
Blokkpolymerisatene a) og deres fremstilling er utførlig The block polymers a) and their preparation are detailed
omtalt i de innledningsvis nevnte publikasjoner. discussed in the initially mentioned publications.
Innen rammen av foreliggende oppfinnelse fremstilles de fortrinnsvis ved at det gåes ut fra en polypropylenglykol med en gjennomsnittlig molekylvekt fra ca. 1500-3500, fortrinnsvis fra ca. 1700-2500, hvortil man i nærvær av alkaliske katalysatorer, fortrinnsvis kaliumhydroksyd, natriumhydroksyd og/eller natriummetylat, tilleirer etylenoksyd inntil det ønskede etylenoksyd-propylenoksyd-blokkpolymerisat foreligger, idet man etter avslutning av adduktdannelsen katalysatoren forblir i produktet, nøytraliseres eller adskilles ved filtrering eller ionutveksling. Within the framework of the present invention, they are preferably produced by starting from a polypropylene glycol with an average molecular weight of approx. 1500-3500, preferably from approx. 1700-2500, to which in the presence of alkaline catalysts, preferably potassium hydroxide, sodium hydroxide and/or sodium methylate, ethylene oxide is deposited until the desired ethylene oxide-propylene oxide block polymer is present, with the catalyst remaining in the product after completion of the adduct formation, neutralized or separated by filtration or ion exchange.
Blokkpolymerisatene a) har en gjennomsnittlig molekylvekt på fortrinnsvis 1900-3800 og et innhold av etylenoksyd på fortrinnsvis 10-30 vekt-% og av propylenoksyd på fortrinnsvis 70-90 vekt-%, hver gang referert til blokkpolymerisatet. The block polymers a) have an average molecular weight of preferably 1900-3800 and a content of ethylene oxide of preferably 10-30% by weight and of propylene oxide of preferably 70-90% by weight, each time referred to the block polymer.
Omsetningen av blokkpolymerisatet a) med formaldehyd foregår ved at de bringes til reaksjon med 0,5 til to ganger, fortrinnsvis 0,8-1,5 ganger støkiometrisk mengde formaldehyd, referert til de i det anvendte blokkpolymerisatet tilstedeværende hydroksyl-grupper (bestemt som hydroksyl-tall), i nærvær av sure katalysatorer og ved en temperatur på 50-180°C, fortrinnsvis 80-160°C. Formaldehydet kan anvendes i form av paraformaldehyd eller i form av en fortrinnsvis 20-40 vekt-% vandig oppløsning (formalin). Det kan også anvendes tilsvar-ende mengde av trioksan. Omsetningen gjennomføres fortrinnsvis således at komponentene a), b) og katalysatoren haes alene (omsetning i stoff) eller sammen med oppløsningsmidlet og oppvarmes under omrøring til den angitte temperatur, idet det dannede reaksjonsvann fjernes. Omsetningen gjennomføres så lenge inntil det ikke eller omtrent ikke dannes mer reaksjonsvann. Det er vanligvis tilfellet etter 3-15 timer. The reaction of the block polymer a) with formaldehyde takes place by bringing them into reaction with 0.5 to two times, preferably 0.8-1.5 times the stoichiometric amount of formaldehyde, referred to the hydroxyl groups present in the block polymer used (determined as hydroxyl -number), in the presence of acid catalysts and at a temperature of 50-180°C, preferably 80-160°C. The formaldehyde can be used in the form of paraformaldehyde or in the form of a preferably 20-40% by weight aqueous solution (formalin). An equivalent amount of trioxane can also be used. The reaction is preferably carried out in such a way that the components a), b) and the catalyst are taken alone (reaction in substance) or together with the solvent and heated with stirring to the specified temperature, the water of reaction formed being removed. The turnover is carried out until no or almost no more water of reaction is formed. This is usually the case after 3-15 hours.
Det kan anvendes uorganiske eller organiske sure katalysatorer. Egnede katalysatorer er eksempelvis halogenhydrogensyrer Inorganic or organic acid catalysts can be used. Suitable catalysts are, for example, hydrohalic acids
som saltsyre og bromhydrogensyre, fosforsyrer, svovelsyre:/sulfonsyrer som p-toluensulfonsyre og dodecylbenzensulfonsyre, halogeneddiksyrer som trikloreddiksyre og trifluor-eddiksyre, perfluorkarboksylsyrer som perfluoroktansyre, perfluorsulfonsyrer som perfluoroktansulfonsyre og blandinger herav. Foretrukne sure katalysatorer er svovelsyre, dode-cylbenzensulf onsyre og para-toluensulfonsyre. Mengden av sure katalysatorer ligger i det katalytiske området og ut-gjør følgelig vanligvis 0,05-3 vekt-%, fortrinnsvis 0,1-1,5 vekt-%, referert til vekten av det anvendte blokkpolymerisat such as hydrochloric acid and hydrobromic acid, phosphoric acids, sulfuric acid:/sulfonic acids such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid, haloacetic acids such as trichloroacetic acid and trifluoroacetic acid, perfluorocarboxylic acids such as perfluorooctanoic acid, perfluorosulfonic acids such as perfluorooctanesulfonic acid and mixtures thereof. Preferred acid catalysts are sulfuric acid, dodecylbenzenesulfonic acid and para-toluenesulfonic acid. The amount of acid catalysts is in the catalytic range and therefore usually amounts to 0.05-3% by weight, preferably 0.1-1.5% by weight, referred to the weight of the block polymer used
a) . a) .
Det dannede reaksjonsvann fjernes, eventuelt etter en forkon-densasjon ved 80-120°C over 1-6 timer, hensiktsmessig under anvendelse av vakuum (vannstrålevakuum) eller ved slepe- The reaction water formed is removed, possibly after a pre-condensation at 80-120°C over 1-6 hours, suitably using a vacuum (water jet vacuum) or by towing
resp. azeotrop destillasjon ved hjelp av et organisk oppløsnings middel. Som organisk oppløsningsmidler_kommer det eksempelvis i betraktning heksan, cykloheksan, toluen, xylen, tetralin, dialkylformaler med 1-4 C-atomer i alkylgruppen, eksempelvis dimetylformal og dibutylformal eller blandinger herav. Foretrukne oppløsningsmidler er toluen, xylen, dialkylformaler med' 1-4 C-atomer pr. alkylgruppe eller blandinger herav. Mengden av oppløsningsmiddel kan variere innen vide grenser. Den retter seg etter anvendt mengde av forbindelse a). respectively azeotropic distillation using an organic solvent. As organic solvents, for example, hexane, cyclohexane, toluene, xylene, tetralin, dialkyl formals with 1-4 C atoms in the alkyl group, for example dimethyl formal and dibutyl formal or mixtures thereof, come into consideration. Preferred solvents are toluene, xylene, dialkyl formals with 1-4 C atoms per alkyl group or mixtures thereof. The amount of solvent can vary within wide limits. It depends on the amount of compound a) used.
Det dannede reaksjonsprodukt befries eventuelt fra anvendt oppløsningsmiddel og nøytraliseres med en til den anvendte syrekatalysator svarende mengde alkali, fortrinnsvis med natriummetylatoppløsning. The formed reaction product is optionally freed from the solvent used and neutralized with an amount of alkali corresponding to the acid catalyst used, preferably with sodium methylate solution.
Forbindelsen som skal anvendes ifølge oppfinnelsen er gulig The compound to be used according to the invention is yellow
til brunfargede, mer eller mindre viskose væsker, som er oppløselige i organiske oppløsningsmidler, eksempelvis i xylen. Disse forbindelser egner seg spesielt fordelaktig til spalting av'jordoljeemulsjoner av typen vann-i-olje, da de fremfor alt har en høy virkning også ved relativt lave opparbeidelsestemperaturer. I jordoljeoppberedningsanlegg oppvarmes vann-i-olje emulsjonene alt etter viskositet til 40-70°C og bringes under tilsetning av egnede demulga-torer (spaltere) eller ved hjelp av en kombinert elektrisk-kjemisk arbeidsmåte til avtagningsspesifikasjonen for raffinerier. to brown-coloured, more or less viscous liquids, which are soluble in organic solvents, for example in xylene. These compounds are particularly advantageously suitable for splitting petroleum emulsions of the water-in-oil type, as above all they have a high effect even at relatively low processing temperatures. In crude oil processing plants, the water-in-oil emulsions are heated, depending on viscosity, to 40-70°C and brought under the addition of suitable demulsifiers (splitters) or by means of a combined electrical-chemical working method to the removal specification for refineries.
Forbindelsene ifølge oppfinnelsen utmerker'seg nå spesielt The compounds according to the invention now stand out in particular
ved at de også ved lavere oppberedningstemperaturer etter korte separingstider gir avtagningsspesifikke råjordoljer og at dertil er det bare nødvendig med en relativ mengde. in that, even at lower preparation temperatures after short separation times, they provide removal-specific raw soil oils and that only a relative amount is required for this.
For denne anvendelse er det hensiktsmessig å fortynne de For this application, it is appropriate to dilute them
nye produkter med oppløsningsmidler. Som oppløsningsmidler new products with solvents. As solvents
anvendes hensiktsmessig alkoholer som metanol, isopropanol og butanol, aromatiske hydrokarboner som toluen og xylen eller handelsvanlige oppløsningsmidler som blandinger av høyere aromater (solventnafta). alcohols such as methanol, isopropanol and butanol, aromatic hydrocarbons such as toluene and xylene or commercial solvents such as mixtures of higher aromatics (solvent naphtha) are suitably used.
De anvendte mengder av forbindelsene ifølge oppfinnelsen som jordoljeemulsjonsspaltere ligger alt etter råjordoljeemulsjonen og oppberedningstemperatur vanligvis ved 5-100 ppm, fortrinnsvis ved 10-50 ppm. The amounts of the compounds according to the invention used as petroleum emulsion splitters are, depending on the crude petroleum emulsion and preparation temperature, usually at 5-100 ppm, preferably at 10-50 ppm.
Oppfinnelsen skal forklares nærmere ved hjelp av noen eksempler. The invention will be explained in more detail with the help of some examples.
Fremstilling av de ved fremgangsmåten ifølge oppfinnelsen52Y§2^kare<_>for^in^elser• Production of the by the method according to the invention
Eksemp_el_l Example_el_l
Blokkpolymerisat (komponent a): Block polymer (component a):
Polypropylenglykol med en gjennomsnittlig molekylvekt på Polypropylene glycol with an average molecular weight of
2000 omsettes på kjent måte i nærvær av alkaliske katalysatorer med så meget etylenoksyd at det fåes et etoksylat med 10 vekt-% etylenoksyd i sluttproduktet (hydroksyl- 2000 is reacted in a known manner in the presence of alkaline catalysts with so much ethylene oxide that an ethoxylate with 10% by weight of ethylene oxide is obtained in the final product (hydroxyl
tall 55). number 55).
120 g av blokkpolymerisatet, 10,6 g 35 vekt-%-ig vandig formalinoppløsning (de 10,6 g tilsvarer to ganger støkio-metrisk mengde formaldehyd, referert til tilstedeværende hydroksylgrupper) og 120 g xylen haes sammen i en rørkolbe som er utstyrt med en utkretsningsoppsats. Etter tilset- 120 g of the block polymer, 10.6 g of 35% by weight aqueous formalin solution (the 10.6 g corresponds to twice the stoichiometric amount of formaldehyde, referred to hydroxyl groups present) and 120 g of xylene are combined in a tube flask equipped with an outline essay. After addi-
ning av 2,1 g dodecylbenzensulfonsyre (det er 1,75 vekt-% referert til vekten av anvendt blokkpolymerisat) oppvarmes under omrøring ved 14 0°C og holdes ved denne temperatur i 6 timer under uttak av reaksjonsvann. Etter avkjøling nøytraliseres reaksjonsproduktet med en Na-metylatoppløs-ning. Det foreligger en lavviskos, gulbrun, ca. 50%-ig xylenisk oppløsning av reaksjonsproduktet. addition of 2.1 g of dodecylbenzenesulfonic acid (it is 1.75% by weight referred to the weight of the block polymer used) is heated with stirring at 140°C and kept at this temperature for 6 hours while withdrawing reaction water. After cooling, the reaction product is neutralized with a sodium methylate solution. There is a low-viscosity, yellowish-brown, approx. 50% xylenic solution of the reaction product.
Eksemp_lene_2-9 Example_lene_2-9
120 g av en propylenoksyd-etylenoksyd-blokkpolymer med en polypropylenglykolkjerne av gjennomsnittlig molekylvekt 2000 og et varierende etylenoksydinnhold -fra 15-50 vekt-% i sluttproduktet (komponent a, fremstilt analogt eksempel 1) oppvarmes hver gang med 120 g xylen, 2,1 g dodecylbenzensulfonsyre (det er 1,75 vekt-%, referert til vekten av anvendt blokkpolymerisat) og de i følgende tabell anvendte mengder av 35%7ig vandig formalinoppløsning (disse mengder er hver gang to ganger støkiometrisk mengde av formaldehyd, referert til tilstedeværende hydroksylgrupper) sammen i rørkolben til 140°C og holdes 6 timer ved denne temperatur, idet dannet vann taes ut. Etter avkjøling til ca. 40°C nøytraliseres som i eksempel 1. 120 g of a propylene oxide-ethylene oxide block polymer with a polypropylene glycol core of average molecular weight 2000 and a varying ethylene oxide content - from 15-50% by weight in the final product (component a, prepared analogously to example 1) is heated each time with 120 g xylene, 2.1 g of dodecylbenzenesulfonic acid (it is 1.75% by weight, referred to the weight of the block polymer used) and the quantities of 35%7ig aqueous formalin solution used in the following table (these quantities are each time twice the stoichiometric amount of formaldehyde, referred to the hydroxyl groups present) together in the tube flask to 140°C and kept at this temperature for 6 hours, the water formed being removed. After cooling to approx. 40°C is neutralized as in example 1.
Man får hver gang en lavviskos, gulbrun, ca. 50%-ig xylenisk oppløsning av sluttproduktet. Each time you get a low-viscosity, yellow-brown, approx. 50% xylenic solution of the final product.
Eksemp<el_>10 Example<el_>10
150 g av en propylenoksyd-etylenoksyd-blokkpolymer med en polypropylenglykolkjerne på gjennomsnittlig molekylvekt 1700 og et etylenoksydinnhold på 27 vekt—% i sluttproduktet (fremstilt analogt eksempel 1 med et hydroksytall på 49) haes med 2,15 g paraformaldehyd 91%-ig sammen i en rørkolbe og under omrøring tilsettes 0,37 g konsentrert svovelsyre (det er 0,25 vekt-% svovelsyre, referert til blokkpolymerisatets vekt). Formaldehydmengden tilsvarer 0,5 mol HCHO pr. tilstedeværende hydroksylgruppe, det er en ganger støkiometrisk mengde. 150 g of a propylene oxide-ethylene oxide block polymer with a polypropylene glycol core of average molecular weight 1700 and an ethylene oxide content of 27% by weight in the final product (produced analogously to example 1 with a hydroxy number of 49) are combined with 2.15 g paraformaldehyde 91% in a flask and, while stirring, 0.37 g of concentrated sulfuric acid is added (it is 0.25% by weight of sulfuric acid, referred to the weight of the block polymer). The amount of formaldehyde corresponds to 0.5 mol HCHO per hydroxyl group present, it is one times stoichiometric amount.
o o
Etter oppvarming til 100 C omrøres 1 time, deretter holdes ved 140°C en ytterligere time og deretter anlegges vannstrålevakuum. Under et vakuum på ca. 2000 Pa omrøres nå^ 6 timer ved 140°C og reaksjonsvannet fjernes. Etter nøytra-lisasjon med Na-metylatoppløsning får man en middelsviskos, brun væske som er godt oppløselig i organiske oppløsnings-midler, f.eks. xylen. After heating to 100°C, stir for 1 hour, then hold at 140°C for a further hour and then apply a water jet vacuum. Under a vacuum of approx. 2000 Pa is now stirred for 6 hours at 140°C and the water of reaction is removed. After neutralization with Na-methylate solution, a medium-viscous, brown liquid is obtained which is well soluble in organic solvents, e.g. xylene.
Eksempel_ll Example_ll
150 g av et blokkpolymerisat med en polypropylenglykol- 150 g of a block polymer with a polypropylene glycol
kjerne av gjennomsnittlig molekylvekt 3200 og et etylenoksydinnhold på 30 vekt-% i sluttproduktet (hydroksyltall 26) bringes til reaksjon med 1,16 g paraformaldehyd 91%-ig og 0,3 g konsentrert svovelsyre (0,2 vekt-%, referert til blokkpolymerisat) som ved eksempel 10. De 1,16 g paraformalde- core of average molecular weight 3200 and an ethylene oxide content of 30% by weight in the final product (hydroxyl number 26) is reacted with 1.16 g of paraformaldehyde 91% and 0.3 g of concentrated sulfuric acid (0.2% by weight, referred to block polymer ) as in example 10. The 1.16 g of paraformaldehyde
hyd tilsvarer 0,5 mol formaldehyd pr. hydroksylgruppe, hyd corresponds to 0.5 mol formaldehyde per hydroxyl group,
det er en ganger støkiometrisk mengde. it is one times the stoichiometric amount.
Det nøytraliserte sluttprodukt er ved 20°C en viskos, mørkebrun væske. The neutralized end product is a viscous, dark brown liquid at 20°C.
Eksempel_12 Example_12
100 g av den i eksempel 10 nevnte blokkpolymer og 50 g av den i eksempel 11 nevnte blokkpolymer bringes til reaksjon med 1,8 g paraformaldehyd (91%-ig) og 0,3 g konsentrert svovelsyre (0,2 vekt-%, referert til blokkpolymerisat) som 100 g of the block polymer mentioned in example 10 and 50 g of the block polymer mentioned in example 11 are reacted with 1.8 g of paraformaldehyde (91% strength) and 0.3 g of concentrated sulfuric acid (0.2% by weight, referred to to block polymer) which
omtalt i eksempel 10. De 1,8 g paraformaldehyd tilsvarer 0,5 mol formaldehyd pr. hydroksylgruppe, det er en gang støkiometrisk mengde. mentioned in example 10. The 1.8 g of paraformaldehyde corresponds to 0.5 mol of formaldehyde per hydroxyl group, it is once stoichiometric amount.
Etter nøytralisering fåes et ved 20°C viskost, brunt produkt som er oppløselig i de vanlige organiske oppløsningsmidler. After neutralization, a viscous, brown product is obtained at 20°C which is soluble in the usual organic solvents.
Anvendelse av forbindelsene foreslått ifølge oppfinnelsen Use of the compounds proposed according to the invention
Eksemp_el_13 Example_el_13
Råoljeprøveemulsjon, det er en råolje fra det sydtyske området som er blitt innstilt til et vanninnhold på 51 vekt-% og en salinitet på 0,25 vekt-%. Crude oil sample emulsion, it is a crude oil from the southern German area that has been adjusted to a water content of 51% by weight and a salinity of 0.25% by weight.
Demulgeringstemperatur: 50°C. Demulsification temperature: 50°C.
Eksem<p>_<e>l_<14> Eczema<p>_<e>l_<14>
Råoljeprøveemulsjon ifølge eksempel 13 Demulgeringstemperatur: 25°C Crude oil sample emulsion according to example 13 Demulsification temperature: 25°C
Claims (6)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813142954 DE3142954A1 (en) | 1981-10-29 | 1981-10-29 | "METHOD FOR SEPARATING WATER-IN-OIL OIL EMULSIONS" |
Publications (1)
Publication Number | Publication Date |
---|---|
NO823593L true NO823593L (en) | 1983-05-02 |
Family
ID=6145142
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO823593A NO823593L (en) | 1981-10-29 | 1982-10-28 | PROCEDURE FOR SEPARATING OIL OIL EMULSES OF THE WATER-I OIL TYPE. |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0078489B1 (en) |
BR (1) | BR8206284A (en) |
DE (2) | DE3142954A1 (en) |
NO (1) | NO823593L (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2609648B1 (en) * | 1987-01-16 | 1990-12-14 | Total France | DESEMULSIFYING AND ANTI-FOULING AGENT CAPABLE OF SEPARATING WATER-HYDROCARBON MIXTURES, WHETHER EMULSIFIED, AND APPLICATIONS THEREOF |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1018179B (en) * | 1956-04-07 | 1957-10-24 | Hoechst Ag | Process for dewatering nassoelen |
DE1495827A1 (en) * | 1964-08-06 | 1969-06-12 | Hoechst Ag | Process for breaking emulsions |
DE2536121A1 (en) * | 1974-08-19 | 1976-03-04 | Basf Wyandotte Corp | SURFACE-ACTIVE BLOCK POLYOXYALKYLENE CO-POLYMERS |
-
1981
- 1981-10-29 DE DE19813142954 patent/DE3142954A1/en not_active Withdrawn
-
1982
- 1982-10-26 DE DE8282109878T patent/DE3267833D1/en not_active Expired
- 1982-10-26 EP EP82109878A patent/EP0078489B1/en not_active Expired
- 1982-10-27 BR BR8206284A patent/BR8206284A/en unknown
- 1982-10-28 NO NO823593A patent/NO823593L/en unknown
Also Published As
Publication number | Publication date |
---|---|
EP0078489A3 (en) | 1984-02-08 |
EP0078489A2 (en) | 1983-05-11 |
DE3142954A1 (en) | 1983-05-11 |
DE3267833D1 (en) | 1986-01-16 |
BR8206284A (en) | 1983-09-20 |
EP0078489B1 (en) | 1985-12-04 |
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