Patent Application: US-201213443662-A

Abstract:
the present invention relates to the application of ionic liquids individually or in formulation to dry and desalt crudes oils having api gravities in the range of 8 to 12 when applied at concentrations ranging from 500 and up to 5000 ppm . the ionic liquids have a cation selected from the group consisting of carboxymethane - ammonium , ammonium , imidazolium , isoquinolinium , pyridinium , and 1 , 5 - dicarboxylic - pentane - 2 - ammonium and an anion selected from the group consisting of r 5 coo − , cl − , br − , − , − , − , − , 31 , − , where r 5 is alkyl , cycloalkyl , benzyl , alkenyl , aromatic or alkyl functionalized between 1 and 18 carbon atoms , and r 6 is methyl or ethyl .

Description:
the present invention relates to the application of different families of il &# 39 ; s and their formulations in the demulsification of median , heavy and extra - heavy crude oils which api gravities are within the range of 8 to 30 . the invention is directed to the use of ionic liquids dissolved in solvents having a boiling point in the range from 35 ° c . to 200 ° c ., preferably dichloromethane , chloroform , methanol , isopropanol , ethanol , benzene , toluene and xylenes , individually or in mixtures of them ; when they are used in concentrations from 50 ppm to 2000 ppm , preferably from 600 ppm until 1750 ppm , even more preferably from 750 ppm to 1500 ppm , to break water in oil emulsions and simultaneously desalt crude oils having and api gravity between 30 and 8 °. the invention is directed to the use of formulations consisting of ionic liquids dissolved in solvents having a boiling point in the range from 35 ° c . to 200 ° c ., preferably dichloromethane , chloroform , methanol , isopropanol , ethanol , benzene , toluene and xylenes , individually or in mixtures of them ; when they are used at concentrations of 50 ppm until 5000 ppm , preferably from 600 ppm to 1750 ppm , even more preferably from 750 ppm to 1500 ppm ; to break water in oil emulsions and simultaneously desalt crude oils having an api gravity between 20 and 8 °. the il &# 39 ; s whose use as demulsifiers and dehydrating claimed in this invention were synthesized , purified and characterized by spectroscopic techniques such as infrared , nmr ( 1h and 13c ) and mass spectrometry , according to the methods described in the literature : martinez r , et al ( 2010 ), flores e a , et al ( 2009 ), tao g h , et al ( 2005 ); himmler s et al ( 2006 ). the il &# 39 ; s used in the present invention have general formula c + a − , where c + is an organic cation represented by 1 , 5 - dicarboxy - pentan - 2 - ammonium , imidazolium , pyridinium , isoquinolinium , ammonium and carboxymethane - ammonium ; and a − is an organic anion , as given in table 1 . different concentrated solutions of each of the il &# 39 ; s were prepared , from 5 to 40 % by weight , using solvents with boiling point falls in the range of 35 to 200 ° c ., preferably dichloromethane , methanol , ethanol , isopropanol , chloroform , benzene , toluene , xylene , turbosine , naphtha , individually or in mixtures of them , so they added small volumes of the dissolution and was avoided that the effect of the solvent influenced in the breakdown of the emulsion . the il &# 39 ; s were evaluated in concentrations falling within the range of 100 to 2000 ppm . the il &# 39 ; s were evaluated simultaneously by way of comparison with commercial formulations of the base type of propylene oxide and ethylene oxide , as demulsifier and desalting agents , table 3 describes the determination of molecular weights ( gpc ) of the commercial copolymers . the evaluated procedure is described below : the number of oblong bottles provided with insert and lid was indicated by the number of compounds to evaluate , over an additional which corresponds to the crude oil without additive ; in each one of them was added crude oil to the 100 ml mark . all the bottles were placed in a bath of water at a controlled temperature in 80 ° c . for 20 minutes , at the end of that time was added the aliquot part of the dissolution of the il &# 39 ; s ( individual or formulations ) and formulations of commercial copolymers mentioned above ; all the bottles were agitated during 3 minutes at a rate of 2 shots per second . after being purged were placed new account in the temperature - controlled bath and the breaking of emulsion water in oil was successively read in the following way : every 5 minutes during the first 60 minutes , every 10 minutes during the second hour , and finally every hour until the end of the test . all the il &# 39 ; s a matter of this invention and commercial formulations were evaluated at different including concentrations in the range 100 to 2000 ppm . by way of demonstration , which does not imply any limitation , are shown in the following figures , the graphical results of the evaluation described above , for different concentrations of both individual and formulated il &# 39 ; s . fig1 shows that the il - 05 after 80 minutes and a concentration of 500 ppm shows the greater water removal in maya crude oil , compared to 1500 to 2000 ppm . at the time of 80 minutes is achieved 85 % of water removal ; at 180 minutes is reached 92 % and from 240 minutes 95 %. in the fig2 is showed that il - 21 efficiently removes the water of the maya crude oil in the interval of concentrations included between 1500 and 2000 ppm . at 25 minutes , both concentrations remove the water in a 50 %, starting from that time the concentration of 2000 ppm showed the best performance in the removal of water reaching 95 % in 180 minutes , however later is observed that the emulsion is formed again . on the other hand , the concentration of 1500 ppm always shows to a tendency to the rise in the removal of water , achieving 95 % to the 360 minutes . in table 4 , the values for the efficiency in the dehydrated and desalted after of the treatment with il &# 39 ; s are shown ( to see fig1 and 2 ). for the il - 06 the values of desalted are very similar although the greater proportion of removed water was obtained with the concentration of 500 ppm . on the other hand , the il - 21 obtained the greater water removal with the concentrations of 1500 and 2000 ppm , however the greater proportion of desalted was obtained with the concentration of 1500 ppm , being also this concentration the one that desalted with greater effectiveness to the mayan crude . in addition , in fig3 it is observed that il &# 39 ; s 05 and 21 break the water / oil emulsion perfectly , because the aspect of the watery phase is clear , is transparent and clots neither thread are not observed , that is to say the interphase is very well defined . with the purpose that the investigation developed in this invention is even more useful to the national system of refineries , we proceeded to evaluate the il &# 39 ; s in crude even heavier ( smaller api gravity ). for this purpose , it is prepared a crude denominated m + t ( api = 17 . 1 ) starting from the combination of 6 volumes of mayan crude oil ( api = 19 . 1 ) and 1 volume of tekel crude oil ( api = 14 . 84 ). the evaluation also included the comparison with two commercial products , one of them is a triblock copolymer of polypropylene oxide — polyethylene oxide of the company z ( z - 1 ) ( mn = 2900 and i = 1 . 07 ) and the other one is a formulation property of the imp ( rhs - 5 ). the results are shown in the following graphics . the il &# 39 ; s 6 , 16 , 17 and 21 break with greater efficiency the emulsion water - oil when compares with imp formulation and the commercial copolymer ; the il - 21 obtained the major efficiency ( 90 %) to the 240 minutes . these results are shown in the fig4 . next the values obtained in the desalted stage are compared with the treatment realized by the il &# 39 ; s and with commercial products . in fig5 , 6 and 7 , it is observed clearly that il &# 39 ; s 16 , 17 and 21 breaks the emulsion water - oil present in heavy crude , because the corresponding interphases are well defined , also the presence of clots and thread are not observed ; particularly , in fig7 the formulation imp - rhs - 5 does not break the emulsion , therefore and considering all before exposed , it is possible to affirm that the il &# 39 ; s before mentioned overcome in dehydrating and desalinating efficiency to the formulations commercial and of the imp . so far it is observed that is greater drying efficiency and therefore the efficiency of desalination of il &# 39 ; s compared to commercial copolymer and the formulation of imp , which consists of breakers , coalescing and clarifiers agents of the emulsion continuing the ils application , they were evaluated in a heavier crude oil ( api = 9 . 2 ); results are shown in the following graphs : the water removal efficiency of il &# 39 ; s 16 , 17 , and 21 , at a concentration of 1500 ppm is reported in fig8 ; it could be observed that the ionic liquid il - 21 removes 90 % of water in less than one hour , this efficiency is greater than those of il - 16 and il - 17 , because they require two hours for removing the same amount of water . a comparative study of the dehydrating and desalting efficiencies of the ionic liquids 16 , 17 and 21 and some commercial copolymers of x and z companies ( x and z copolymers respectively ). it may be easily observed in fig9 that il &# 39 ; s 16 , 17 and 21 ( 1500 ppm ) break an emulsion faster than commercial copolymers z - 1 , 2 and 3 ( 1000 ppm ); although il &# 39 ; s are employed at a greater concentration , their efficiencies justify them , as the best copolymer , z - 2 , reach just 70 % of water removal . a similar behavior is observed in fig1 , that is to say , il &# 39 ; s show better performance that those of commercial copolymers , now from x company ; best of them reached an efficiency of 80 %, lower than those of il &# 39 ; s yield . in the table 6 are summarized the percentages of desalting and dewatering of il &# 39 ; s 16 , 17 and 21 , compared to those of commercial copolymers provided by z and x companies ; it is clear that the performance of the il &# 39 ; s are better in both aspects . fig1 shows bottles which show that water - oil interfaces are well defined after the application of il &# 39 ; s 16 and 17 over an extra - heavy crude oil ( 9 . 2 api ), however some lumps are observed on the bottle wall . different formulations were obtained from combinations of il &# 39 ; s 16 , 17 and 21 at different compositions ; the performance of these formulations is reported in fig1 and it can be observed that at a total concentration of 1000 ppm ( 500 ppm of each ionic liquid ) there was a water removal of 90 % before 120 minutes . in fig1 is showed the synergy between il &# 39 ; s when they are combined in formulations , at 1000 ppm ( total concentration ) the performance reached in dewatering is 90 %, similar value obtained by il &# 39 ; s when they were evaluated at 1500 ppm in independent way , as it is reported in fig1 . it is also important to remark that formulations , which performance is reported in fig1 , remove water more efficiently that commercial copolymers z - 2 and x - 2 . finally , it may be observed in table 7 that the dehydrating and desalting efficiencies of il &# 39 ; s are greater than those of formulations prepared with commercial products from x and z companies . al - sabagh a m , badawi a m and noor ei - den m . r . 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