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)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2003
  • 2003-06-04 DE DE10325198A patent/DE10325198B4/de not_active Expired - Fee Related
• 2004
  • 2004-05-25 US US10/559,719 patent/US7671098B2/en active Active
  • 2004-05-25 DE DE502004004384T patent/DE502004004384D1/de not_active Expired - Lifetime
  • 2004-05-25 WO PCT/EP2004/005587 patent/WO2004108863A1/de active IP Right Grant
  • 2004-05-25 EP EP04734666A patent/EP1658356B1/de not_active Expired - Fee Related
• 2005
  • 2005-12-21 NO NO20056114A patent/NO336950B1/no not_active IP Right Cessation

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