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 invention relates to petroleum emulsion splitters based on alkoxylated polyethyleneimines and processes for demulsifying petroleum emulsions, in which the petroleum emulsion splitters according to the invention are used.
• Oil and water emulsions are produced in large quantities during the extraction and processing of crude oil, with the continuous outer phase depending on the proportions of water to oil, the natural emulsifier system contained in the oil and the history of the emulsion's origin.
• the majority of the crude oil is produced as a water-in-oil emulsion and has to be split by adding chemical demulsifiers.
• block polymers of ethylene and / or propylene oxide as splitters for water-in-oil emulsions.
• German published application 15 45 250 e.g. a dewatering process is known in which various alkylene oxide polymers and compounds derived therefrom with hydrophilic end groups are added to the water-in-oil emulsions, but these are not yet fully effective at high temperatures and often only at elevated temperatures. However, after use, they leave too much residual water, residual salt or residual emulsion, and above all they are only sufficiently effective with a few special types of oil.
• the water-in-oil emulsions are often heated with high energy consumption in order to then achieve the low water, salt and possibly residual emulsions required for further processing by chemical or electro-chemical methods.
• water-in-oil emulsions can be split without heating even at the temperatures at which they are conveyed, ie between 10 ° C. and 40 ° C., with the addition of suitable splitters.
• DE-OS 22 27 546 teaches that rapid dewatering of crude oils can be achieved by the addition of demulsifying substances based on derivatives of polyalkylene oxides.
• the process is characterized in that at least one polyalkylene polyamine with at least two recurring alkyleneimine units in the molecule is added to the crude oils at least one polyalkylene polyamine which is fully alkylated 10 to 300 times on the nitrogen atoms.
• the salt water separated in this way still contains certain amounts of residual oil, with oil-in-water emulsions preferably forming.
• the amount of emulsified crude oil in the oil-in-water emulsions can be up to 5%.
• demulsifiers so-called deoilers, which are mostly cationic polymers, such as those e.g. be described in DE-34 04 538. Typical products are also described in U.S. Patents 4,333,947 and 3,893,615.
• DE 24 35 714 A1 teaches to completely quaternize polyalkylene polyamines, as are known from DE-OS 22 27 546. This additional process step is complex, however, and should therefore also be avoided for cost reasons.
• the present invention was therefore based on the object of providing petroleum emulsion splitters which not only bring about good splitting of water-in-oil emulsions, but also lead to the water which is split off containing as little residual oil as possible and which are as simple to produce as possible .
• petroleum emulsion splitters based on alkoxylated polyethyleneimines which are characterized in that they are obtained by alkoxylating a polyethyleneimine with a molecular weight (weight average M w ) of 2,500 to 35,000 with 5 to 40 moles of propylene oxide and 5 to 40 moles of ethylene oxide can be obtained per ethyleneimine unit in the polyethyleneimine.
• crude oil emulsion splitters are known which are produced by alkoxylation, especially with ethylene and propylene oxide, of polyalkylene polyamines, but the quantitative ratios of alkylene oxide to polyalkylene polyamine given there include a very wide range (10 to 300 times alkoxylation of each Nitrogen atom) and according to the examples, polyethyleneimines with a MW of 2,100 to 86,000, reacted with 70 to 95 moles of propylene oxide and 20 to 28 moles of ethylene oxide, are used.
• Emulsion splitters are preferred, for their preparation polyethyleneimines with a molecular weight M w of 5,000 to 25,000 are used and which are obtained by alkoxylation of the polyethyleneimines with 5 to 30 moles of propylene oxide and 5 to 20 moles of ethylene oxide, in each case based on an ethyleneimine unit in the polyethyleneimine .
• the emulsion splitters according to the invention also have the advantage that they contain no metal salts, in particular corrosion-promoting chlorides.
• the invention also relates to a process for the demulsification of petroleum emulsions, in which the emulsion at temperatures of 10 ° C to 130 ° C, preferably at 50 ° C to 80 ° C, with the petroleum emulsion splitter according to the invention or with solutions containing the petroleum emulsion splitter included, treated.
• the emulsion splitters are prepared in a manner known per se in a one- or multi-stage, preferably two-stage, procedure.
• an alkaline catalyst such as sodium methylate, potassium tert-butoxide, potassium hydroxide, sodium hydroxide, basic ion exchanger and others added, followed by further oxalkylation with the required amounts of alkylene oxide at about 125 ° C to 135 ° C.
• the reaction can be carried out, for example, by pressing on the entire amount of the alkylene oxide in the presence of water-containing or -free alkaline catalyst and allowing it to react at temperatures between 125 ° C. and 135 ° C.
• a higher proportion of by-products, such as pure polyalkylene glycol ethers, can occur here, but this has no significant influence on the desired properties of the products.
• the ratio of propylene oxide to ethylene oxide can be varied in the ranges given above.
• Starting products for the preparation of the compounds to be added according to the invention are generally known polyethyleneimines, prepared in a conventional manner from ethyleneimine. The stated molecular weights were determined by light scattering.
• the emulsion splitters according to the invention can also be used together with other emulsion splitters, e.g. with the alkoxylated alkylphenol formaldehyde resins known from DE-OS 27 19 978.
• the splitters are preferred because of their associated better meterability than solutions with 20 to 90% by weight splitters.
• Mixtures of organic solvents e.g. methanol
• organic solvents e.g. Toluene, xylenes, tetrahydrofuran, dioxane, C1-C13 alcohols, glycols and light petroleum fractions of the boiling point mentioned.
• solutions these are expediently adjusted to an active substance content (splitter content) of 40 to 60% by weight or 70 to 90% by weight.
• splitter content active substance content
• the solutions are preferred to crude oils added to the probes (in the field).
• the cleavage then already takes place at the temperature of the freshly pumped water-in-oil emulsion at such a rate that the emulsion can be broken on the way to the processing plant. There it is separated in a possibly heated separator and possibly with the help of an electric field without difficulty into pure oil and salt water.
• the splitters are expediently added to the crude oil emulsions in amounts (active ingredient) of 0.1 to 200 ppm, preferably 5 to 50 ppm, based on the weight of the emulsion to be split, at temperatures between 10 ° C. and 130 ° C., preferably 50 ° C to 80 ° C added.
• the rapid breakers to be used according to the invention can be used for water-in-oil emulsions with about 0.1 to 99% by weight salt water content. Crude oil emulsions of various origins come into consideration as oils that can be drained quickly in this way.
• the splitter A produced according to the synthesis example is added in an amount of 25 ppm to three different crude oil emulsions from West Africa at 40 ° C. with stirring, and the samples are then left to stand. The separated amounts of water were measured after certain time intervals.
• the oil emulsions having a splitter B which had been prepared by alkoxylation of polyethyleneimine with a molecular weight of about 21,000 (M w) with 36 moles of ethylene oxide and 86 moles of propylene oxide per ethyleneimine were placed in the manner indicated above. The results are shown in Table I.
• 100 ml of the petroleum emulsion to be tested was filled into 177.44 ml, graduated, clearly transparent test bottles with a rectangular cross section. 25 ppm by weight of the demulsifier were added to the emulsions in the test bottles.
• the test bottles containing the samples to be tested were shaken 100 times and then evaluated for water clarity according to the evaluation criteria given below.
• the petroleum emulsion splitter according to the invention behaves advantageously with regard to its splitting properties (Table I) compared to a comparison substance which differs from the splitter according to the invention essentially by a significantly higher degree of propoxylation.
• the splitter according to the invention achieves very good separation of the residual oil from the separated water (Table II).

Landscapes

• 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)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Polyethers (AREA)
• Colloid Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Applications Claiming Priority (2)

Publications (3)

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Cited By (9)

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• 1991
  • 1991-11-07 DE DE4136661A patent/DE4136661A1/de not_active Withdrawn
• 1992
  • 1992-10-31 EP EP92118674A patent/EP0541018B1/fr not_active Expired - Lifetime
  • 1992-10-31 DE DE59204911T patent/DE59204911D1/de not_active Expired - Fee Related
  • 1992-11-04 US US07/971,201 patent/US5445765A/en not_active Expired - Lifetime
  • 1992-11-06 JP JP4297023A patent/JPH05305204A/ja not_active Withdrawn
  • 1992-11-06 NO NO924294A patent/NO303987B1/no not_active IP Right Cessation
  • 1992-11-06 CA CA002082287A patent/CA2082287A1/fr not_active Abandoned

Patent Citations (1)

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