EP1658356B1 - Alkoxylierte vernetzte polyglycerine und ihre verwendung als biologisch abbaubare emulsionsspalter - Google Patents
Alkoxylierte vernetzte polyglycerine und ihre verwendung als biologisch abbaubare emulsionsspalter Download PDFInfo
- Publication number
- EP1658356B1 EP1658356B1 EP04734666A EP04734666A EP1658356B1 EP 1658356 B1 EP1658356 B1 EP 1658356B1 EP 04734666 A EP04734666 A EP 04734666A EP 04734666 A EP04734666 A EP 04734666A EP 1658356 B1 EP1658356 B1 EP 1658356B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ether
- alkoxylated
- polyglycerols
- diglycidyl ether
- glycerol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000223 polyglycerol Polymers 0.000 title claims description 45
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 34
- 239000000839 emulsion Substances 0.000 claims description 28
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 27
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 18
- 235000019198 oils Nutrition 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 claims description 6
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000002118 epoxides Chemical class 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- HIGURUTWFKYJCH-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1(COCC2OC2)CCCCC1 HIGURUTWFKYJCH-UHFFFAOYSA-N 0.000 claims description 2
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- HAZWONBCJXKAMF-UHFFFAOYSA-N 2-[1-[1,3-bis[2-(oxiran-2-ylmethoxy)propoxy]propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC(OCC(C)OCC1OC1)COCC(C)OCC1CO1 HAZWONBCJXKAMF-UHFFFAOYSA-N 0.000 claims 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims 1
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 claims 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims 1
- 239000004359 castor oil Substances 0.000 claims 1
- 235000019438 castor oil Nutrition 0.000 claims 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims 1
- 229920001451 polypropylene glycol Polymers 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 235000011187 glycerol Nutrition 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 239000010779 crude oil Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- WOKDXPHSIQRTJF-UHFFFAOYSA-N 3-[3-[3-[3-[3-[3-[3-[3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)CO WOKDXPHSIQRTJF-UHFFFAOYSA-N 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 4
- -1 for example Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003849 aromatic solvent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002477 conductometry Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
Definitions
- the present invention relates to the use of alkoxylated crosslinked polyglycerols for the splitting of water-oil emulsions, in particular in crude oil production.
- Crude oil accumulates in its promotion as an emulsion with water. Before further processing of the crude oil these crude oil emulsions must be split into the oil and water content. For this purpose, one generally uses so-called petroleum splitters. Petroleum breakers are surface-active polymeric compounds capable of effecting, within a short time, the required separation of the emulsion components.
- alkoxylated glycerin as a demulsifying ingredient in lubricating oils has been disclosed in US 5,256,064 DD-229 006 described.
- glycerol is reacted with alkylene oxides to either a block copolymer or a random copolymer.
- alkoxylated di- and triglycerols as petroleum emulsion breakers has also been described ( U.S. 3,110,737 . US 2,944,982 such as U.S. 4,342,657 ).
- Alkoxylated polyglycerols are known per se. They are described in the prior art for various applications. For example, in U.S. 5,502,219 alkoxylated polyglycerols esterified to produce a low calorie substitute for vegetable oils. In U.S. 4,061,684 For example, the alkoxylated polyglycerols were esterified and used as water-swelling gels. Alkoxylated polyglycerols reacted with alpha olefin epoxides act accordingly WO-98/03243 as a defoamer. Sulfation of alkoxylated polyglycerols leads to substances used in hair shampoos, such as U.S. 4,263,178 disclosed.
- Alkoxylated polyglycerols have been used in DE 101 07 880 A1 disclosed as effective emulsion breakers.
- alkoxylated crosslinked polyglycerols show excellent action as petroleum breakers even at very low dosage. In addition, they showed significantly better biological Degradability (according to OECD 306) compared to conventional commercial emulsion breakers and alkoxylated non-crosslinked polyglycerols.
- the invention therefore relates to the use of alkoxylated polyglycerols crosslinked with multifunctional electrophilic compounds and having a molecular weight of from 1000 to 100,000 units comprising from 5 to 100 glycerol units alkoxylated with C 2 -C 4 -alkylene oxide groups or a mixture of such alkylene oxide groups such that the crosslinked, alkoxylated polyglycerol has a degree of alkoxylation of from 1 to 100 alkylene oxide units per free OH group, to cleave oil / water emulsions in amounts of 0.0001 to 5 wt .-%, based on the oil content of the emulsion to be cleaved.
- alkoxylated crosslinked polyglycerols are obtainable from crosslinked polyglycerols having 5 to 100 glycerol units by alkoxylation of the free OH groups with a C 2 -C 4 -alkylene oxide or a mixture of such alkylene oxides in a molar excess, so that the alkoxylated crosslinked polyglycerol has the stated degree of alkoxylation.
- the preparation of the polyglycerol is known in the art and is generally carried out by acid or alkali catalyzed condensation of glycerol.
- the reaction temperature is generally between 150 and 300 ° C, preferably at 200 to 250 ° C.
- the reaction is usually carried out at atmospheric pressure.
- the catalyzing acids for example, HCl, H 2 SO 4 , sulfonic acids or H 3 PO 4 are mentioned, as bases NaOH or KOH, which are used in amounts of 0.1 to 50 wt .-%, based on the weight of the reaction mixture.
- the condensation generally takes 3 to 10 hours.
- Polyglycerols can be represented by formula 1.
- n is the degree of condensation, ie the number of glycerol units. n increases with increasing reaction time and is determined by OH number.
- the polyglycerols thus prepared are crosslinked with di- or multifunctional, electrophilic compounds. This achieves a very easily controllable increase in the molecular weight of the polyglycerols.
- Suitable crosslinkers include di- or polyglycidyl ethers, di- or polyepoxides, di- or polycarboxylic acids, carboxylic anhydrides, di- or polyisocyanates, dialkoxydialkylsilanes, trialkoxyalkylsilanes and tetraalkoxysilanes. The crosslinking is carried out as known in the art.
- crosslinkers are particularly preferred:
- crosslinkers or chemically related compounds mentioned are preferably used in the range of 0.1-10, more preferably 0.5-5 and especially 1.0-2.5% by weight, based on the polyglycerol.
- the crosslinking step is carried out after the glycerol condensation and before the alkoxylation.
- Crosslinking after glycerol condensation and subsequent alkoxylation can According to the invention also be carried out.
- the crosslinked polyglycerols obtained from glycerol condensation and subsequent crosslinking are then alkoxylated with one or more C 2 -C 4 -alkylene oxides, preferably ethylene oxide (EO) or propylene oxide (PO).
- EO ethylene oxide
- PO propylene oxide
- the alkoxylating agent is used in molar excess.
- the alkoxylation is carried out, as known in the art, by reacting the polyglycerols with an alkylene oxide under elevated pressure of generally 1.1 to 20 bar at temperatures of 50 to 200 ° C.
- the alkoxylation takes place on the free OH groups of the polyglycerols. So much alkylene oxide is used that the average degree of alkoxylation is between 1 and 100 alkylene oxide units per free OH group. By medium degree of alkoxylation is meant here the average number of alkoxy units which is attached to each free OH group. It is preferably from 2 to 70, especially from 5 to 50, especially from 20 to 40.
- the alkoxylation is carried out first with PO and then with EO.
- the ratio of EO to PO in the alkoxylated polyglycerol is preferably between 1: 1 and 1:10.
- the alkoxylation can also be carried out in the reverse order, first EO then PO or with a mixture of PO and EO.
- the polyglycerol obtained after condensation, subsequent crosslinking and alkoxylation preferably has a molecular weight of from 3,000 to 50,000 units, in particular from 5,000 to 30,000 units, especially from 8,000 to 25,000.
- (AO) k , l, m O are the alkoxylated OH radicals in which AO is a C 2 -C 4 -alkylene oxide unit and k, l, m are the degrees of alkoxylation.
- n stands for the degree of condensation of glycerol. n is preferably a number from 5 to 50, more preferably 8 to 30, especially 10 to 20.
- a preferred subject of the present invention is the use of the alkoxylated polyglycerols as a splitter for oil / water emulsions in petroleum production.
- the cross-linked alkoxylated polyglycerols are added to the water-oil emulsions, preferably in solution.
- solvents for the crosslinked alkoxylated polyglycerols paraffinic or aromatic solvents are preferred.
- the crosslinked alkoxylated polyglycerols are used in amounts of 0.0001 to 5, preferably 0.0005 to 2, in particular 0.0008 to 1 and especially 0.001 to 0.1 wt .-% based on the oil content of the emulsion to be cleaved.
- the crosslinked polyglycerols described above were introduced into a 1 l glass autoclave and the pressure in the autoclave was brought to about 10 bar with nitrogen. 0.2 bar overpressure set. It was slowly heated to 140 ° C and after reaching this temperature, the pressure is again set to 0.2 bar overpressure. Thereafter, the desired amount of EO (see Table 1) was added at 140 ° C, the pressure should not exceed 4.5 bar. After completion of EO addition was allowed to react for 30 minutes at 140 ° C.
- the crosslinked polyglycerols described above were introduced into a 1 l glass autoclave and the pressure in the autoclave was adjusted to about 0.2 bar overpressure with nitrogen. It was slowly heated to 130 ° C and after reaching this temperature, the pressure is again set to 0.2 bar overpressure. Thereafter, the desired amount of PO was metered in at 130 ° C. (see Table 1), the pressure not exceeding 4.0 bar. After completion of the addition of PO was allowed to react for 30 minutes at 130 ° C.
- the degree of alkoxylation was determined by means of 13 C-NMR.
- emulsion breaker To determine the effectiveness of an emulsion breaker, the water separation from a crude oil emulsion per time and the drainage and desalting of the oil was determined.
- 100 ml of the crude oil emulsion were introduced into breaker glasses (conically tapered, screwable, graduated glass bottles), in each case a defined amount of the emulsion separator was metered with a micropipette just below the surface of the oil emulsion, and the breaker was mixed into the emulsion by intensive shaking. Thereafter, the breaker glasses were placed in a tempering bath (30 ° C and 50 ° C) and followed by the separation of water.
- samples were taken from the oil from the upper part of the splitter glass (so-called top oil) and the water content according to Karl Fischer and the salt content were determined by conductometry.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10325198A DE10325198B4 (de) | 2003-06-04 | 2003-06-04 | Verwendung von alkoxylierten vernetzten Polyglycerinen als biologisch abbaubare Emulsionsspalter |
PCT/EP2004/005587 WO2004108863A1 (de) | 2003-06-04 | 2004-05-25 | Alkoxylierte vernetzte polyglycerine und ihre verwendung als biologisch abbaubare emulsionsspalter |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1658356A1 EP1658356A1 (de) | 2006-05-24 |
EP1658356B1 true EP1658356B1 (de) | 2007-07-18 |
Family
ID=33494818
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04734666A Expired - Lifetime EP1658356B1 (de) | 2003-06-04 | 2004-05-25 | Alkoxylierte vernetzte polyglycerine und ihre verwendung als biologisch abbaubare emulsionsspalter |
Country Status (5)
Country | Link |
---|---|
US (1) | US7671098B2 (no) |
EP (1) | EP1658356B1 (no) |
DE (2) | DE10325198B4 (no) |
NO (1) | NO336950B1 (no) |
WO (1) | WO2004108863A1 (no) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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RU2539897C2 (ru) | 2009-07-30 | 2015-01-27 | Басф Се | Композиция для нанесения металлического покрытия, содержащая подавляющий агент, для беспустотного заполнения субмикронных элементов поверхности |
DE102009041983A1 (de) | 2009-09-17 | 2011-04-07 | Clariant International Ltd. | Alkoxylierte Trialkanolaminkondensate und deren Verwendung als Emulsionsspalter |
DE102009042971A1 (de) | 2009-09-24 | 2011-09-15 | Clariant International Ltd. | Alkoxylierte cyclische Diamine und deren Verwendung als Emulsionsspalter |
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BR112013012214A2 (pt) | 2010-11-17 | 2019-09-24 | Dow Brasil Sudeste Ind | método para desestabilizar uma emulsão de petróleo bruto/água |
DE102012005377A1 (de) | 2012-03-16 | 2013-03-14 | Clariant International Ltd. | Alkoxylierte Polyamidoamine und deren Verwendung als Emulsionsspalter |
DE102012005279A1 (de) | 2012-03-16 | 2013-03-14 | Clariant International Limited | Alkoxylierte, vernetzte Polyamidoamine und deren Verwendung als Emulsionsspalter |
CA2870885C (en) * | 2012-05-31 | 2019-06-25 | Nalco Company | Glycerol based polymer surface active chemistry and production |
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US5667727A (en) * | 1995-06-26 | 1997-09-16 | Baker Hughes Incorporated | Polymer compositions for demulsifying crude oil |
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DE10107880B4 (de) * | 2001-02-20 | 2007-12-06 | Clariant Produkte (Deutschland) Gmbh | Alkoxylierte Polyglycerine und ihre Verwendung als Emulsionsspalter |
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DE502004004384D1 (de) | 2007-08-30 |
EP1658356A1 (de) | 2006-05-24 |
DE10325198A1 (de) | 2005-01-13 |
WO2004108863A1 (de) | 2004-12-16 |
US7671098B2 (en) | 2010-03-02 |
NO20056114L (no) | 2005-12-21 |
DE10325198B4 (de) | 2007-10-25 |
US20060281931A1 (en) | 2006-12-14 |
NO336950B1 (no) | 2015-11-30 |
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