• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A relatively nonvolatile, high molecular weight sulfur solvent produced by adding at least 40 parts by weight of elemental sulfur per 100 parts by weight dialkyl disulfide to an amine activated dialkyl disulfide oil. Such a sulfur solvent is particularly useful in sustaining a liquid phase at bottomhole conditions for high temperature, high pressure wells.
    公开号:SU1085512A3
    申请号:SU813235490
    申请日:1981-01-28
    公开日:1984-04-07
    发明作者:П.Шарп Шелби；Ярбороф Лаймэн
    申请人:Стандарт Ойл Компани (Фирма)；
    IPC主号:
    专利说明:

    eo DI
    SP
    Yu

    This invention relates to methods for dissolving elemental sulfur deposits in wells.
    During the processing and production of gas with a high content of hydrogen sulfide and elemental sulfur, the latter accumulates in the wells and on the walls of communications, resulting in blockage of reservoirs, columns of compression-air pipes installed on the surface of the equipment 1, and thereby reducing gas extraction from the wells. In this connection, various methods are used to prevent the precipitation of elemental sulfur and the removal of sulfur plugs during operation.
    Methods are known for removing deposits of elemental sulfur in wells, based on the ability of sulfur to form polysulfides, in particular, the treatment of wells with a solution of alkali metal or ammonium hydroxides interacting with hydrogen sulfide; contained in the gas to form sulfide, which then extracts sulfur in the form of polysulphide l.
    The closest to the proposed technical day and the achieved result is the method of removing elemental sulfur from the well and from the walls of communications q using a solvent. As the latter, a mixture of a liquid unsubstituted aliphatic amine, the molecule of which contains 4-12 C atoms (for example, diethylamine), is used with a disulfide, the molecule of which contains 4-22 C atoms, in particular with R-S-R type disulfide, where R is an alkyl group. The solvent is prepared in such a proportion that the amount of amine in the mixture is 610% of the value of the disulfide. The resulting mixture before pumping into the well or communication stand for 3090 days 2.
    This solvent exhibits exceptional ability in relation to. dissolving sulfur, but loses its efficiency for ultra-deep sour gas with high temperature and high pressure.
    With the increase in global energy consumption and with the onset of an international shortage of fuel for the oil and gas industry, transition to drilling deeper and deeper wells in increasingly severe environmental conditions in search of scarce fuel.
    The purpose of the invention is to provide an opportunity to work in conditions of high temperatures and high pressures.
    The goal is achieved by haem, which according to the method of removing
    elemental sulfur deposits in the wells by introducing a sulfur solvent containing a mixture of dialkyl disulfide and amine into them, which are introduced in an amount of up to 27 wt.h. on 100 ma.ch. dialkyl disulfide and in addition elemental sulfur in an amount of at least 40 parts by weight. on 100 ma.ch. dialkyl disulfide.
    In this case, the solvent is injected into the well in such a way as to ensure the constant presence of a liquid phase at the bottom of the well.
    There are 3 possible uses of the invention:
    1. The solvent is injected into the wellbore zone and the well, and the operation is suspended to allow the solvent to be absorbed and remove sulfur deposits.
    2. A small but effective amount of solvent is continuously injected into the bottomhole zone or production string during operation in order to remove sulfur deposits and inhibit or prevent further formation of sulfur deposits.
    3. The presence of sulfur deposits is monitored and, as necessary for a particular well, continuous injection is alternated with an imbibing method.
    When a sufficient amount of sulfur is added to the dialkyl dieulfide, a heavy alkyl polysulfide oil is formed that is capable of condensing in the liquid phase under the conditions of the bottom of a sour gas. The fatty amine chemically binds to the dialkyl disulfide to form a high molecular compound with a low volatility, so that the liquid phase exists at high temperature and high pressure.
    By adjusting the amount of fatty amine, the degree of volatility can be adjusted by adjusting the properties of the composition to the needs of a particular gas well, thereby ensuring that the liquid phase is present in the bottom hole conditions.
    Dialkyl disulfides suitable as a starting component for obtaining a sulfur solvent are compounds with the formula R-S-R-R, such as dimethyl disulfide, diethyl disulfide, dioctyl disulfide, ditertiary tetradecyldisulfide.
    Liquid base aliphatic amines are suitable for activating dialkyl disulfides at a concentration of up to 10% by weight under conditions of long exposure to dialkyl disulfide for chemical
    incorporation into dialkis ciculphide. By adjusting the vapor pressure of the relatively volatile aliphatic amine during activation amine dialkyl (e.g., diethylamine) and by repeating this measurement at a gradually increasing amounts of amine was We mention cluded obviously 2 mol dnalkildisulfida per 1 mole of the amine nitrogen has upper stoichiometric amount of the amine that is chemically can be embedded in amine-activated dialkyl disulfide plant sulfur. Under the conditions described for the use of low molecular weight aliphatic amines, the upper stoichiometric ratio roughly corresponds to 10% by weight of the amine.
    It has been found that achieving a complete stoichiometric concentration of amine nitrogen is highly desirable and, therefore, values above 10 wt.h. amine per 100 math. Dialkyl disulfide (in particular, 27 parts by weight, amine) are advantageous for the purposes of the invention.
    The most suitable amines are (diethylamine, triethylamine, diisopropylamine, 2-hexycans, butylamine, hexylamine, octylamine, dodecylamine and N-alkyl-1, 3-propanediamines (RNH2CH2CH2CH2NH2) under the trade name Duomeen R, under the trade name Duomeen R, under the trade name Duomeen R, under the trade name Duomeen R and
    Example. Activating the dialkyl disulfide by adding amine, get the target alkyl polysul | feed oil in the subsequent dissolution of elemental sulfur in the activated amine cm disulfide oil. The solubility and rate of dissolution of sulfur in dialkyl disulfide amines varies somewhat depending on the source of sulfur, the particular physical state, the degree of grinding. However, for the purposes of this invention, the NIN is suitable for any free element sulfur. The dissolution process can be accomplished using conventional techniques, i the best technique is soft heat with stirring. The CEC of the amount of dissolved sulfur varies in accordance with the requirements of the particular gas well being treated. In principle, the more severe the conditions at the wellhead, the sulfur content. A significant amount of the liquid phase under the conditions of the bottom hole can be obtained using 40- 60 mas. Hours. sulfur per 100 mach. dialkyldieulfide, with a particularly desirable amount of 80 wt.h. eery 100 ma.ch. dialkyl disulfide, and the resulting solution is well handled, stored and transported under ambient conditions without noticeable deposition (deposition) of sulfur or visillinosity, a tendency to cure. Although in terms of creating the required amount of liquid phase for dissolving sulfur, higher concentrations of sulfur are preferable, but in the case of cold environmental conditions or during cold periods of the year, it may be necessary to specifically add 40 wt. eernogo raetvora. High concentrations of eers can be necessary in only European levels, i.e. at extreme temperatures. In the literature there are flashes for the case in which the concentration of 500 g of sulfur per 100 g of dialkyl disulfide was reached. However, when implementing the invention, it is remembered that this reference describes the essential solubility of sulfur, therefore, upon receipt of the proposed formulations, it is necessary to install it shortly before evaluating sulfur to get the solvent ery.
    The presence of a liquid alkyl polyol sulfide phase in the presence of a dry raw gas at high temperatures and high pressures is of paramount condition for the dissolution of elemental sulfur. In order to psd confirm the presence of the target liquid phase under the conditions of this well, one conducts a series of experiments on the phase determination of a variable volume in a PVT cell with a window. These data, relative to the receipt of different alkylpolyol sulfide oils, are listed in Table 1.
    Table
    The first two forms are prepared by applying a pressure of 7.1 g of diethylamine to 100 g of Herox disulfide oil. ; Grinded sulfur is added to this mixture by activating the Merox solution without any noticeable exposure. The other three samples are derived from Meryox aliquots (diethylamine mixture prepared in accordance with method 2). To these superior samples, ground elemental sulfur is added. In all cases, the dissolution of sulfur is carried out by heating and by obligatory shaking. After cooling to room temperature, only a sample showed a slight tendency to sulfur precipitation. Thus, this-- "The northen solution can be used at ambient sulfur temperatures. The data obtained also show that the aged samples compared with fresh samples are capable of absorbing higher concentrations of sulfur without showing a tendency to sulfur deposition at room temperature. All tested samples showed a pour point below (-12 ° C). Under extreme conditions and with higher concentrations of sulfur, the temperature i is controlled by steam supply to the fire.1, external heating or internal heating, insulation, etc. Thus, for convenience, it is preferable to use about 30 grams of sulfur per 100 grams of disulfide, however, higher concentrations may be necessary, especially in high-sulfur gas wells at ultrahigh temperatures and pressures. The first and fifth samples were tested in the presence of dry sulfur dioxide in a PVT cell of variable volume with a window under high pressure at 285 ° F (). When conducting phase-distribution circuits, the composition of sulfur dioxide is selected and the temperature is chosen so that they meet the operating conditions of 1M, where there is a problem of sulfur deposition (a gas well on sour gas produces ecologic 1 MMSCF gas per hour and about 114 kg of elemental sulfur are deposited at the mouth per hour (1 MflSCF 28-10 nm). The first investigated amine alkylpolysulfide oil was first prepared by adding 7.1 g of dystiLemin to 100 g of fresh Carox disulfide oil, then in this dialkyl disulfide ma After dissolving 80 g of crushed sulfur with gentle heating to 190®F (88 ° C) and mild stirring. For the purposes of this invention, we will call samples of this type non-sustained or fresh solvent. After cooling the fresh solvent to room temperature, about 75 ° F (24 ° С) 10 cm aliquot of the solvent will be placed in a variable volume cell with an okouzh and 2 g-mol (47 g) of dry sulfur dioxide will be injected into this cell under the pressure of 1500 pSi (105 atm), the composition of which is the following, mol%: N2 4, CH 62} CO 9; HjS 25. This particular formulation corresponds to 37.4-25 barrels of alkyl polysulphide oil, injected into a high-sulfur gas well per million standard cubic feet of extraction 37.3 lb of oil / MP SCF sulfur dioxide 0.213 L / Nm 1,016 1,702 2,359 3,050 4,068 4,567 5,190 6,175 7,238 8,202 15.8 bbt oil / mm SCF sernis 1,6621321.64
    1 p Sia 0.07 atm. As can be seen from Table 2, the liquid phase 60 is always present over the entire pressure range. Data on the ratio of the volume of the liquid network at the specified temperature and pressure to the volume of the introduced sulfur dioxide, 10 bore sour gas (1 bbe / M iSCF 5, l / nm). The cell is kept at (I4lc), while the volume is changed in such a way that the pressure in the cell varies from about 1000 to 3200 pSia (from 70 to 574 atm). The total cell volume. And the volume of liquid phase present in whose cell are recorded at various pressures. Table 2 presents the results of the experiments on the distribution of phases for fresh amine-activated alkyl polysulfide oil with tasoM sulfur (), table 2 16 35 feed oils are of practical importance for calculating the treatment process of a washed well, which reflect the relative volume of the liquid phase . pressure (depth) in the well at the injection of 37.4 barrels of oil to MMSCF dry gas withdrawn from the well: for example, at a pressure of 8000 pSia (560 atm) about 44% of the injected fluid in the liquid state, at the end of the study on the distribution of the phases, the cell is returned to the lower value of the pressure range, and an additional 2.7 g-mol (63.5 g) of sulfur dioxide is introduced in order to ensure a compositional ratio of 15.8 Lb 1 / MMSCF (0.09 l / nm After receiving data on this point, the window cell was depressurized and the experiment was stopped (data on this additional point are included in Table 2). Although in this case only one measurement was performed with composite OTHOL-15.7 bbE / MMSCF, it was found that there is a significant amount of liquid vapor However, it is assumed that reducing the amount of injected fluid more than doubles will ensure the presence of a significant amount of the required liquid phase in wellhead conditions. The second series of phase distribution experiments are carried out using an amine-activated dialkyl disulfide oil prepared in accordance with the known method 2J. 110 g of crushed sulfur (sample 5, Table 1) are added to 100 g of a sample aged with diethylamine-activated dialkyl disulfide oil (Merox mixture). The mixture is heated to about 200 ° F (93, with necessary mixing until the sulfur is dissolved. After cooling 3.14 bbt of oil / M ZSR, the sulfur dioxide is
    sulfur dioxide at 140 C)
    1,845 1127,640,8
    679.40
    3.050 4.120 577.07
    432.05 379.28 342.86
    0.421
    0.384
    0.73 0.342 0.65
    0.342 0.368 0.368 to room temperature 75F {24 C) 1.90 cm aliquot is placed in a variable volume cell with a window along with 4.55 mol of sulfur dioxide, injected under pressure of 1110 pSia (77.7 at). The ratio of 3.14 bbf / tlMSCF of 0.0166 l / nm corresponds to the performance of the solvent injection equipment available for the high-sulfur gas under consideration. In this case, the cell volume is varied so that the pressure varies from about 1800 pSia to above 7000 pSla (from 126 to 490 atm). It has been noted that there is a significant amount of liquid phase in the entire pressure range. After completing the phase distribution experiments, the cell with a window is returned to the lower part of the pressure range and inject additional quantity of an addercanic dialkyl polysulfide oil activated by diethylamine (1.90 cm at 75 and 1900 pSi) into it, thereby providing a 6.28 bb / fMSCF- ratio ( 0.0358 l / nm). The phase distribution experiments are repeated at this higher concentration of alkyl polysulfide oil. After the completion of these experiments, the PVT cell with OKoiTjKOM is cooled to 113F (45 C) and the data are measured at two additional points. These last two points mimic possible typical conditions in a separator located after the head of a high-sulfur gas well. Table 3 presents the results of the experiments on the distribution of the phases for the aged activated alkyl polysulfide oil with sour gas. Table 3 285 F (0.018 L / Nm6, 28 L8 oil / MUZSG sulfur dioxide at Table 3, along with the data on the phase distribution of alkyl polysulfide oils, for comparing them with the known compositions, presents the distribution of the phases for the amine-activated Merox 40 disulfide oil without elemental sulfur. The composition of sulfurous gas, mol.%: CH4 58; CO 18, HjS 24. The experiments were carried out according to the described method in a variable volume cell with an okouzh, but at the well temperature in the wellhead (149 C), the data on the phase distribution collected at those different formulations, corresponding to t-50 vuuih 297.3 barrels of activated Merox to tWSCF sulfur dioxide, 196.4 bbB / IUlSCF and 75.6 Li / MMSCP (1.7; 1.12 and 0.43 l / nm). Two different Disulfide oil source Merox 55. Experience at 297.8 lb / hshzsr and 75.6 bbf / flKSCF was carried out using merox, produced by gulf oils torner wally plzit (Gu6f Valley PEant), whereas the experience with 196.4 bbE / The IWSCF is carried out using Merox disulfide mixture produced by Warren HeTpojjeyMC Eyat Plant (Warren Petroleums In ay town Ptant).
    (Continuation of Table 3 285 (0.0358 l / nm) Comparison of the data shows that a small difference in temperatures, the composition of sulfur dioxide and the WepOKc source of dialkyl disulfide oil does not have a large effect on the results. At the same time, the presence of pre-introduced sulfur in dialkyl disulfide oil causes a dramatic change in phase behavior. At pressures of approximately 4250 pSia (297 atm), the liquid phase does not exist, unless about 300 barrels of Merox are pumped into the MMSCF into it. 1.71 liters of gas to be removed deletion ex sulfur can be achieved. Thus, the known dialkyl disulfide oils as a whole cannot serve as sulfur diluents in deep wells of sulphurous gas at high temperatures and high pressures, if no more than 300 bar relay p is inserted in them, the solvent is on SCP we select the gas (1.71 l / nm). However, in practice, the injection of 300 barrels on the MLMR is unachievable. The data show that the amount of liquid phase present at high temperature and high pressures typical of wellhead conditions increasing It is due to the presence of sulfur. Therefore, the addition of sulfur to the disulfide oil greatly reduces the volatility of the oil, with the result that the necessary liquid phase exists even at high temperatures and high pressures. When producing the alkyl polysulfide oil according to the invention, the amount of sulfur pre-activated in the amine-activated disulfide oil should be sufficient to reduce the volatility of the oil to ensure the presence of a liquid phase at temperatures and pressures typical of the particular well. In deep wells of hot sulfur dioxide, in which there is no liquid condensate, it is about 40-60 g of dissolved sulfur per 100 g of disulfide oil. Preferably, the amount is 80 grams of sulfur per 100 grams of disulfide, since this practically does not result in deposition of sulfur at average ambient sulfur temperatures and solutions are obtained that are easily transported and stored. However, higher concentrations are also used, especially at higher temperatures and pressures when lower elasticities are needed. The proposed method makes it possible to remove the sulfur deposits in the wells, operating under conditions of high temperatures and high pressures.
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR REMOVING SLEEP-ELEMENTARY SULFUR DEPOSITS IN WELLS by introducing into them a solvent containing dialkyl disulfide and an amine with 4 ~ с 12 · characterized in that, in order to enable the process to be carried out at high temperatures and pressures, amine ~ is introduced in an amount of up to 27 parts by weight per 100 parts by weight dialkyl disulfide and, in addition, elemental sulfur in an amount of at least 40 parts by weight is added to the solvent. per 100 parts by weight dialkyl disulfide.
    [2]
    2. The method according to claim 1, characterized. the fact that the solvent is introduced into the well in such a way as to ensure a constant presence of a liquid phase at the bottom of the well. § ω s
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    引用文献:
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    BRPI0923461A2|2008-12-23|2016-01-12|Basf Se|process for compressing a gas stream comprising hydrogen sulfide, and using a mixture|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/043,520|US4248717A|1979-05-29|1979-05-29|Method for removing elemental sulfur from high temperature, high pressure wells and flow lines|
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