• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    An aqueous composition is provided, suitable for direct use in waterflood oil recovery processes, which comprises the clarified fermentation fluid obtained by (a) culturing a polysaccharide-producing microorganism in an aqueous culture medium to produce an aqueous culture containing dissolved polysaccharide therein; and (b) clarifying the resultant aqueous culture from (a) by at least one of centrifugation and filtration, introducing therein at least one bactericidal agent, and recovering the resultant clarified fermentation fluid; said aqueous composition being obtained without precipitation and recovery of a solid polysaccharide and dissolution thereof in an aqueous medium. The above composition can be pumped into oil formations without substantial clogging thereof.
    公开号:SU1001866A3
    申请号:SU782632147
    申请日:1978-07-03
    公开日:1983-02-28
    发明作者:Баллерини Даниель；Шоде Одиль；Шовето Ги；Колер Норбер；Вандекастель Жан-Поль
    申请人:Энститю Франсэ Дю Петроль (Фирма)；Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    Vital buffer for the injection of micellar emulsions. The preparation of fermentation media is carried out by fermentation according to known methods. The most suitable microorganism is Hapthamonas campestris. Fermentation is interrupted when a sufficient concentration of the biopolymer in the solution is reached, which is easily determined by viscosity measurement, then the microbial cell is separated by solid, liquid fractionation, as for example. By filtering through layers of diatomaceous earth or a calibrated filter, for example, of the Millipore type. Filtering surfaces or filtering agents with a pore diameter equal to or less than 3 m are preferred, preferably below 1 micron. The preferred embodiment concludes with the implementation of this fractionation by centrifugation, in particular from 4000 g, mainly from 600060000 g. It has been established that the solutions obtained by ultracentrifugation have a lower tendency to clogging of the porous medium, even lower than that obtained simple filtering. The solution of the biopolymer is predominantly stabilized — against possible bacterial decomposition by the addition of bactericides such as sodium azide, formaldehyde, alkaline salts of chlorophenols, such as those sold by the company Ron-Poulenc under the trademark Cryptogil, some salts of mercury, for example, ethyl mercury thiosalicylates, ethyl salts, and salts of phenol mercury (for example, acetam, borate, nitrate) chlorhexidine, 1,2-benzisothiazolone, sold by Imperial Chemical Industries under the brand name Proksel AB Peyt, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3 - he sold by the firm ohm and Haas under the name Cato, etc. A preferred embodiment of the invention is to stabilize the wort, purify cellular debris by adding sodium azide (NaN), which is used, for example, from 10 to 2000 parts by weight. per million (ppm), preferably from 100 to 1000 ppm. Another preferred embodiment is the use of Cato in a preferred amount of from 10 to. 1000 ppm It has been established, although it cannot yet be explained, that these two compounds not only have a protective bactericidal effect, they also have a direct effect on the ability of the media to pass through the porous medium. This action did not work with such a high degree with the usual bactericides. in particular, if some bactericides are equivalent when they are tested on the surface, their different behavior is observed in the presence of deposit bacteria, in contact with elements of this deposit (stone, water, oil). The biopolymer solution may be stored in storage tanks and transported to the well by any suitable means. The biopolymer solution can be adjusted to the desired concentration or viscosity by diluting with deposit water or brine. Useful concentrations of the biopolymer are typically 0.005 and 1.0 wt.%, Preferably 0.050, 25 wt.%. Such concentrations are provided in water containing varying amounts of salts with a viscosity of at least 2 cP at the formation temperature, but in some cases viscosity of about 30 cP or more can be used. Such viscosities are usually sufficient to effectively reduce the mobility of the injected water. If necessary, the pH of the biopolymer solution can be adjusted to equilibrium pH with the formation and control of oxygen content. The biopolymer solution treated in this way can then be pumped into the oil reservoir through one or several injection wells in the usual manner. The leak test was conducted as follows. In order to detect the phenomenon of clogging in the field conditions, the biopolymer solution prepared under standard conditions is first purified by filtration with a constant load of 1 kg / cm on 3 Millipore filters (Millipore Filter Corporation, Bedford, Mass, USA) with a diameter of 142 mm, then on a Millipore 0.8 / 4 filter of the same size. The biopolymer solution is freed from almost all bacterial residues and is therefore completely transparent. Then, using a pump, this purified solution is introduced at a constant rate through a Millipore filter with a pore diameter above 0.8 / J. This insertion is made at rates corresponding to those found inside the formation. Using a differential pressure sensor, the load loss and filter are recorded as a function of time. If necessary, the viscosity of the various fractions at the inlet and outlet of the filter can be measured. In parallel with this leakage test, it is possible to introduce the same biopolymer, purified as described above, into a porous medium with a pore diameter that can be compared with the diameter of the Millipore filter used. A measurement of the pressure loss at the inlet and at the outlet of this porous medium was also made and a conclusion was made on the ability to clog various polysaccharide solutions. All results on leakage, as well as comparative testing on the introduction into the porous medium, are expressed in a decrease in the detectable susceptibility of 6OAHs to the growth of the PCicTeopq biopolymer of the Cheopolmer biopolymer Cheops dissolved, where k is the permeability of the filter or the corresponding liquid porous medium, e; 1 - viscosity of the same liquids. In practice, it is shown that R corresponds to the flow rate indicated with respect to the loss of pressure through a filter or porous solution of a polysaccharide solution, on the one hand, and dissolving water, on the other hand, under the same pH conditions and temperature. . Figures 1 and 2 show the magnitude of the decrease in the mobility of R versus the volume V, expressed in cm, of the polysaccharide solution injected through a Millipore filter, according to Examples 1-6 below, of which examples 3 and 6 characterize the proposed composition, and Examples 1, 2, 4, 5 are given as a comparison. Example 1. A commercial powder lysaccharide (Kelzan MF) sold by Kelco and synthesized by the action of Xanthamonas campestris microorganism on carbohydrates is dispersed by a conventional method in brine containing 5 g of NaCB at pH 8, previously filtered on a Millipore 0.22 filter . The concentration of the polysaccharide in this solution is adjusted to 400 ppm by dilution using the same pre-filtered brine to keep the solution at rest in a nitrogen atmosphere for 24 hours in an appropriate reservoir. Then filtering is performed at a load of 1 kg / cm2 of this solution, first of all, into 3 Millipore 3; 0 filters and with a diameter of 142 mm, and then on a Millipore filter 0.8 / J and with the same diameter. This cleaning treatment aims to free the solution from bacterial residues. Then this solution is introduced by means of a pump at a constant flow rate, corresponding to an increase of 0.25 m / day, through a Millipore filter 3,, O and with a diameter of 47 mm, and the content in the filter carrier is maintained at a constant temperature of 90 °. Loss of load at the entrance and exit of the filter over time is measured and the curve of decrease in mobility R is plotted depending on the volume injected (curve 1, figure 1). It has been found that R rises very quickly with the volume injected and reaches values of the order of 850 and 1360 per 100 and 200 cm of the injected solution. The solution, identical to the previous one, is prepared and prefiltered under the same conditions as described above, and contains a bactericide (sodium azide with 0.04 wt.%), It is introduced at a constant speed of 0.05 m / day in The Fonteblo sandstone core is 2 cm long and 5 cm in diameter, the water permeability is approximately 45 millidarcies, the porosity is 9%. The development of head loss at the ends of this core is measured and a conclusion is drawn on a decrease in the mobility of the Cc. It is established that this decrease in mobility increases very rapidly depending on the number of pore volumes (Vp) of the Kelzan solution injected with a relative viscosity of 2.1 (Table 1). The Kelzan MG solution, freed from bacterial residues, simultaneously clogs the Millipore 3 / filter and the permeability comparison medium. This clogging takes place despite the preliminary cleaning of the polysaccharide solution by passing under strong pressure through 3 Millipore 3 filters and the filter O, 8, t | , I. Example 2. The test on the introduction of the Millipore filters was applied under experimental conditions identical to those of Example 1 with Xanflod, a polysaccharide powder. used at the field and used by Ksanko, the oil department of Kelko. It has been established (Fig. 1, curve 2) that the decrease in mobility increases with the volume injected and reaches a value in the order of 400 out of 100 and 200 cm of solution injected at a constant speed of 0.25 m / day through the Millipore filter 3 /. Example 3: A solution of a biopolymer of the Xanthan type was prepared by fermentation using Xanthamonas campestris strain / NRRb in 1459, obtained from U.S.D.A. (US Department of Agriculture). A nutrient medium is used which has the following composition, g / l: Peptone4 Yeast extract 3 Malcextract 3 K2. HP045. MgS040.5 Glucose30 Distilled Water Up to 1 L (to be filled) The Xanthamonas campestris strain is first grown in agar-agar tubes (nutrient medium agar-agar with 1 wt.%) For several days at. Using a similar tube, a Ferbach flask containing 250 ml of sterilized medium is seeded and stirred for 72 hours on a variable stirrer at. After this time, the concentration of bacterial cells is approximately 3 g / (dry weight). A larger portion of the cells was separated by centrifugation at a load of 30,000 g (20 mi). the viscosity of the solution, measured using a Brookfield viscometer type LVT (25 ° C, 30 vol / module 4), is 390 cP. The concentration of the respective read policy, measured by weighing after sedimentation, preparation, then drying, is approximately 1.4 g / l. then 0.04 wt.% (volume of azide, sodium is added to the solution) and diluted in brine, distilled water plus 5 g / l NaCB, so that the polysaccharide content is approximately 400 ppm and the viscosity is approximately 2 cP. . As for Example 1, this raw biopolymer solution is then cleaned by passing, s first, through 3 Millipore 3 filters and then through a Millipore 0.8 filter / at a constant pressure of 1 kg / cm. Then, this solution is introduced using a pump at a rate corresponding to a constant circulation rate of 0.25 m / day, Millipore filter 3 /, the experimental circuit is the same as the circuit of Example 1. The load loss is measured at and the output of the filter as a function of time and make up the reduction curve R /, depending on the input volume V (curve 3, figs. 1 and 2). It has been established that K remains constant depending on the volume injected and this is despite the relatively higher volume injected than in Experiments 1 and 2. Direct use of the fermentation medium, previously purified and stabilized using an effective bactericide, but without the presence of polysaccharide powder form, therefore, does not give rise to clogging of the Millipore filter 3 /. Example 4. In the fraction of the fermentation solution obtained in Example 3, or in a new fermentation solution prepared under the conditions of this example and freed from the maximum cell portion by centrifugation, the biopolymer was added by adding pure methanol so that its concentration in the final mixture was about 50 wt.%. The precipitate thus obtained is filtered, then washed with pure methanol. The isolated polysaccharide is then redissolved in a solution with 5 g / l NaCt at a concentration of 400 ppm and subjected to a flow test at a constant flow rate through the Millipore 3 filter. Curve 4 (FIG. 2) is obtained, which shows a constant increase in mobility n depending on the volume of L / injected R 2000 to 480 cm in solution, dim solution. Example 5. Another fraction of the polysaccharide obtained in Example 3 is dried in an oven (60 ° C) for 16 hours. The resulting product is then redissolved and brought to a concentration of 400 ppm in solution with 5 g / l NaC8. Subject the resulting solution to a leak test at a constant flow rate through a Millipore 3 / J filter and obtain curve 5 (Fig. 2), which also shows a constant increase in Hn. Get, for example, the value of E ,, equal to approximately 200 to 600 cm of the injected solution. Example 6. A solution of the same biopolymer is prepared as in Example 3, but more concentrated. For this purpose, Xanthamonas campestris (strain NRR / in 1459), as in Example 3, is cultured in Fernbach flasks. Behind- . They use these flasks (2 flasks of 250 ml each) for sowing into a fermenter with a useful volume of 3 liters, equipped for operation with a sterile aerated medium and also equipped with pH and temperature control systems. The travel speed is 1100 rpm, air flow 0.5VVm (air volume / reactor volume / min), temperature. The pH is maintained at 6.5 by the automatic addition of a normal KOH solution. After some time of fermentation, additional glucose is also added, introducing it gradually into the solution using a pump. A total of 50 g / l of glucose was used for the fermentation. The results corresponding to this fermentation are shown in table 2.
    After 70 hours, the viscosity was always measured with a Brookfield viscometer under the same conditions as described above, it was 10,700 s according to the concentration of the biopolymer, always measured by weighing after sedimentation, washing and drying and was 22.8 g / l
    The fermentation medium, after centrifuging at 30,000 g (20 min. At 5 ° C) and adding 0.04 wt.% To one volume of sodium azide, was diluted to a viscosity condition close to that of Example 3, then treated and tested as indicated in this example. Curve 6 (Fig. 2) is obtained which practically does not show clogging after the supply of 600 cm of the injected solution from the Millipore 3 filter.
    Another part of this fermentation filtrate, freed from cell debris by centrifugation at 30,000 g (20 min at) was also diluted to pore volumes (Vi), cm 0.8 11.2 15.4 26.5 32.4 Decrease in mobility (R) 1.69 4.03 i, 29 4.9 5.2
    viscosity close to that of the previous examples, was then purified, as in example 1, by passing at a pressure of 1 kg / cm through 3 filters 3XJ, then through a filter 0.8 / V.
    This bactericidal solution (sodium azide, 0.04 wt.% Vol.) Was injected at a constant rate of 0.05 m / day into the core of the Fonteblo sandstone, identical to Example 1. The progression of head loss at the ends of this core was measured and a conclusion was made on the development of reduced mobility R ,. It is established that this decrease in mobility slowly increases depending on the number of pore volumes of the filtrate of the culture fluid with relative viscosity and 2 (Table 3), in order to stabilize at the end to R, which is slightly lower than 4 by more than 170 input pore volumes.
    Comparing the results table. 3 about the result table. 1, it was found that the fermentation medium, centrifuged and protected with an effective bactericide, clogs the porous medium significantly less than the commercial powder product used in such conditions.
    Table 1
    Table 2 41.7 47 58.2 73 79 HoPs 118; 7.3 8 „7 14.8 18.1 20.9 28.7 30.7
    Pore volume (Vp), cm 1 2.4 5.2 15.0 23.0 30.5 Decrease in mobility (R) 2.33 2.44 2.50 2.84 2.95 3.18
    权利要求:
    Claims (2)
    [1]
    Table 3 60.8 81.4 99.7 127 173 3.75 3.81 3.86 3.92 3.92 Claim 1. An oil displacement composition comprising a polysaccharide solution and an additive, characterized in that to increase the filtration properties of the composition, the filtrate of the culture fluid of the Xanthamonas campestris microorganism producing the polysaccharide is used as a polysaccharide solution, and the bactericidal agent is used as an additive, the components being taken in the following proportions, parts by weight. The filtrate of the culture fluid 100 Bactericidal agent 0,001-0,2
    RM
    1500
    GO O O
    SOO 2. The composition according to claim 1, is also distinguished by the use of sodium azide as a bactericidal agent. 3. The composition according to claim 1, characterized in that a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one in an amount of 0.001-0 is used as a bactericidal agent. , 1 weight.h. Sources of information taken into account in the examination 1.US Patent W 3766983, cl. 166-274, pub. 10/23/73.
    [2]
    2. US patent number 3532166, cl.166-274, published. 06.10.70. 7S-0
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7723008A|FR2398874B1|1977-07-25|1977-07-25|
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