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AZ9RBAYCAN KÍMYA JURNALI № 2 2016
UDC 622.276.5
USING NANODEMULSIFIERS FOR DEMULSIFICATION OF THE OIL EMULSIONS IS ONE OF PRIORITY DIRECTIONS OF MODERN OIL-FIELD CHEMISTRY
T.K.Dashdiyeva
Azerbaijan State University of Oil and Industry [email protected] Received 04.01. 2016
The article presents the results of laboratory and experiment-industrial tests of compositions of nanodemulsifiers "IKHLAS"-1-42 (based on high- and low-molecular surfactants) on the oil fields "Zhetybai" and "Zhanaozen" the Republic of Kazakhstan. According to the results of industrial test, concluded that "IKHLAS"-1 compared with the base demulsifier "Randem"2219, has a significant technological, environmental and economic advantages. Therefore, nanodemulsifier "IKHLAS"-1 was recommended by us (with an optimal dose of ~160 g/t) for a broad introduction at the oil-field "Zhetybaymunaygaz", as well as in other similar oil-fields, in which there are problems, during primary preparation of stable oil emulsions.
Keywords: oilfield chemistry, hard destructible water-oil emulsions, nanodemulsifiers, desuspensifiers, nanoparticles, nonionic surface-active substances.
Transition of oil-fields to the late stage of development is characterized by a significant deterioration of the structure, a continuous increase in the proportion of oil reserves, flooding of crude oil. Thus formed, a stable water-oil inverse, direct and multiple emulsions, which are complicate the processes of preparation of oil and water, leading to the formation of stable intermediate layers in equipments and tanks for preparation oil. Thus, the development and introduction of high-efficiency demulsifiers for old-fields, is one of priority directions oil-field chemistry [1-4].
Experimental part
As objects of study there are used 42 new compositions of nanodemulsifiers under code-names "IKHLAS"-1VIKHLAS"-42, which are protected by a patent [5]. Demulsifiers are composed of various compositions of low-molecular and high-molecular colloidal and non-colloidal non-ionic surface-active agents (surfactants), which possess nano-micellar properties. Experimental part includes the results of laboratory and experiment-industrial tests. Tables 1 and 2 show the results of laboratory tests of these de-mulsifiers on the oil-fields "Zhetybai" and "Zhanaozen" of the Republic of Kazakhstan. Efficiency of demulsifiers was assessed by a
standard "Bottle Test", taking into account relevant requirements GOST R 51858-2002 (mass fractions of water - no more than 0.5%, of chloride salts - no more than 100 mg/dm , mechanical impurities - no more than 0.05%) [1, 3]. The ability of demulsifiers as desuspensifiers of hard destructible of water-oil suspensions (HDWOS), inhibitors hard destructible of water-oil emulsions (HDWOE), has been determined by visual and analytical methods [1].
In the period 03.11.14-03.12.14 there were held experiment-industrial tests (EIT) of demulsifier "IKHLAS"-1, which was chosen specifically for the demulsification of emulsions of a water-oil (W/O), as well oil-water (O/W) in conditions of the shop for primary preparation of oil (SPPO) of oil-field "Zhetybaimunaygas". The purpose of the EIT - determination of the effectiveness of the emulsion breaker "IKHLAS"-1, which consists in preventing the formation and accumulation of HDWOE in the process tanks (as well in water-tanks), ensuring stable operation of the SPPO for the preparation and timely delivery of planned commercial volumes of oil. On the SPPO there was delivered and used 184 barrels (32.000 t) of demulsifier "IKHLAS"-1. Table 3 presents the results of the EIT.
Table 1. The results of laboratory testing new demulsifiers (mark "IKHLAS") at the oil-field "Zhetybai" groups (conditions of test: initial water - 40-43%; temperature - 640C, the specific consumption of demulsifiers - 150 g/t, standing time t = 3.5 hours)_
Name of the demulsifier Water in oil, mg/l Salts in the oil, mg/l The mechanical impurities in oil, % Ability of the desuspensifier Ability of the inhibitor HDWOE Oil in water, mg/l
"IKHLAS"-1 footprints 11 0.004 + + 16
"IKHLAS"-2 0.12 37 0.01 + + 33
"IKHLAS"-3 0.06 23 0.01 + + 32
"IKHLAS"-4 0.18 44 0.02 + + 45
"IKHLAS"-5 0.15 36 0.01 + + 16
"IKHLAS"-6 0.09 26 0.01 + + 39
"IKHLAS"-7 0.12 29 0.02 + + 43
"IKHLAS"-8 0.34 58 0.01 + + 48
"IKHLAS"-9 0.07 14 0.009 + + 28
"IKHLAS"-10 0.21 45 0.02 + + 49
"IKHLAS"-11 0.09 22 0.01 + + 24
"IKHLAS"-12 0.12 29 0.02 + + 31
"IKHLAS"-13 0.17 42 0.03 + + 25
"IKHLAS"-14 0.12 35 0.01 + + 37
"IKHLAS"-15 0.10 23 0.01 + + 20
"IKHLAS"-16 0.09 29 0.02 + + 41
"IKHLAS"-17 0.36 76 0.03 + + 47
"IKHLAS"-18 0.27 48 0.01 + + 24
"IKHLAS"-19 0.40 89 0.03 + + 45
"IKHLAS"-20 0.38 91 0.04 + + 43
"IKHLAS"-21 0.12 29 0.02 + + 19
"IKHLAS"-22 0.32 69 0.01 + + 38
"IKHLAS"-23 0.15 29 0.01 + + 33
"IKHLAS"-24 0.41 87 0.025 + + 50
"IKHLAS"-25 0.06 19 0.02 + + 24
"IKHLAS"-26 0.06 23 0.02 + + 17
"IKHLAS"-27 0.10 34 0.01 + + 33
"IKHLAS"-28 0.38 79 0.04 + + 40
"IKHLAS"-29 0.44 91 0.03 + + 45
"IKHLAS"-30 0.25 53 0.03 + + 46
"IKHLAS"-31 0.24 35 0.01 + + 32
"IKHLAS"-32 0.09 16 0.005 + + 20
"IKHLAS"-3 0.12 29 0.02 + + 39
"IKHLAS"-34 0.19 15 0.01 + + 35
"IKHLAS"-35 0.32 55 0.01 + + 47
"IKHLAS"-36 0.09 16 0.009 + + 18
"IKHLAS"-37 0.07 20 0.006 + + 19
"IKHLAS"-38 0.27 46 0.01 + + 35
"IKHLAS"-39 0.18 49 0.2 + + 43
"IKHLAS"-40 0.43 92 0.04 + + 47
"IKHLAS"-41 0.39 88 0.04 + + 39
"IKHLAS"-42 0.36 74 0.03 + + 44
Prototype [5] 0.83 4.23 0.07 - - 184
Table 2. The results of laboratory testing of new demulsifiers (mark "IKHLAS") at the oil-field "Zhanaozen" (conditions of test: initial water - 13-14%, temperature - 680C, the specific consumption of demulsifiers - 160 g/t, standing time t=1 hour)_
Name of the demulsifier Water in oil, mg/l Salts in the oil, mg/l The mechanical impurities in oil, % Ability of the desuspensifier Ability of the inhibitor HDWOE Oil in water, mg/l
"IKHLAS"-1 footprints 11 0.008 + + 12
"IKHLAS"-2 0.15 40 0.01 + + 31
"IKHLAS"-3 0.09 16 0.01 + + 28
"IKHLAS"-4 0.12 35 0.01 + + 37
"IKHLAS"-5 0.17 42 0.01 + + 33
"IKHLAS"-6 0.14 50 0.02 + + 21
"IKHLAS"-7 0.10 25 0.01 + + 40
"IKHLAS"-8 0.08 19 0.02 + + 46
"IKHLAS"-9 0.18 54 0.007 + + 25
"IKHLAS"-10 0.04 9 0.01 + + 19
"IKHLAS"-11 0.10 36 0.01 + + 28
"IKHLAS"-12 0.18 47 0.01 + + 34
"IKHLAS"-13 0.12 30 0.02 + + 21
"IKHLAS"-14 0.15 39 0.02 + + 47
"IKHLAS"-15 0.09 16 0.01 + + 24
"IKHLAS"-16 0.13 21 0.01 + + 36
"IKHLAS"-17 0.24 54 0.02 + + 45
"IKHLAS"-18 0.33 66 0.01 + + 31
"IKHLAS"-19 0.25 71 0.01 + + 45
"IKHLAS"-20 0.43 98 0.01 + + 48
"IKHLAS"-21 0.15 46 0.01 + + 23
"IKHLAS"-22 0.09 17 0.007 + + 27
"IKHLAS"-23 0.17 53 0.01 + + 39
"IKHLAS"-24 0.44 92 0.03 + + 46
"IKHLAS"-25 0.15 38 0.02 + + 24
"IKHLAS"-26 0.05 20 0.005 + + 15
"IKHLAS"-27 0.27 51 0.01 + + 36
"IKHLAS"-28 0.48 92 0.04 + + 45
"IKHLAS"-29 0.09 18 0.03 + + 22
"IKHLAS"-30 0.17 45 0.03 + + 30
"IKHLAS"-31 0.23 43 0.01 + + 39
"IKHLAS"-32 0.11 27 0.005 + + 18
"IKHLAS"-3 0.18 40 0.02 + + 33
"IKHLAS"-34 0.09 19 0.008 + + 25
"IKHLAS"-35 0.37 68 0.02 + + 40
"IKHLAS"-36 0.16 32 0.01 + + 28
"IKHLAS"-37 0.15 29 0.01 + + 19
"IKHLAS"-38 0.06 18 0.006 + + 35
"IKHLAS"-39 0.45 84 0.2 + + 43
"IKHLAS"-40 0.34 73 0.03 + + 44
"IKHLAS"-41 0.06 21 0.005 + + 31
"IKHLAS"-42 0.25 60 0.02 + + 22
Prototype [5] 0.90 449 0.09 - - 198
Table 3. Results EIT of nanodemulsifier "IKHLAS"-1 in comparison with the basic demulsifier "Randem" 2219 at the oil field "Zhetybai" of the Republic of Kazakhstan_
Parameters "Randem" 2219 "IKHLAS"-1
specific consumption of demulsifier, g/t 204 178
minimum and maximum concentration of chloride salts in running samples RVS №13, mg/l 41-460 12-151
minimum and maximum concentration of water in running samples RVS №13, % 0.12-1.2 0.03-0.27
dominant concentration of water in running samples RVS №13, % 0.15-0.21 0.03-0.09
dominant concentration of chloride salts in running samples RVS №13, % 50-65 20-40
minimum and maximum concentration of chloride salts in running samples RVS №1, mg/l 168-4582 65-1741
minimum and maximum concentration of water in running samples RVS №1, % 0.3-5.2 0.03-1.0
dominant concentration of water in running samples RVS №1, % 0.4-0.7 0.09-0.27
dominant concentration of chloride salts in running samples RVS №1, mg/l 400-600 200-500
minimum and maximum concentration of chloride salts in commercial oil, mg/l 30-5778 28-100
minimum and maximum concentration of water in commercial oil, % 0.09-10 0.06-0.5
dominant concentration of water in commercial oil, % 0.18-0.27 0.09-0.12
dominant concentration of chloride salts in commercial oil, mg/l 45-703 5-45
the average daily consumption of Volga water, m3 777.4 595.0
number of analyzes of commercial oil, results which do not meet the requirements of GOST (within one month) 26 2
period of continuous work RVS 13, days 15 without stopping
average oil concentration in the waste water, which is sent to the system to maintain reservoir pressure (MRP), mg/l 104-14-104 30-50
Results and discussion
Results of laboratory tests
The results of laboratory tests revealed that demulsifiers of "IKHLAS" mark exhibit the highest efficiency compared to the base de-mulsifiers "Randem" 2219. Therefore, results of laboratory tests allow to recommend these compositions for use as [1-6]:
• demulsifiers for inverse and direct emulsions;
• demulsifiers and inhibitors for HDWOE;
• demulsifiers - desuspensifiers for preparation of extracting oil bottom sediments of technological and commercial tanks;
• demulsifiers for pipeline demulsification;
• demulsifiers for inside-downhole demulsification;
• demulsifiers-desuspensifiers for preparation of the barn (trapped) oil;
• demulsifiers-desuspensifiers for preparation of the trapped oil;
• inhibitors of paraffin deposits;
• reagents to restore the permeability of bot-tomhole zone of well;
• reagents of depressants;
• corrosion inhibitors.
The results of the EIT
• "IKHLAS"-1 under all difficult conditions EIT is the first to show the possibilities for simultaneous demulsification of emulsions, water-in-oil (W/O) and oil in water (O/W);
• "IKHLAS"-1 showed high of effectiveness in preventing the formation and accumulation HDWOE in the technological tanks (as well in water-tanks);
• successful implementation of the EIT in conditions of adding HDWOE;
• ensuring stable operation of the SPPO for preparation of crude oil and timely delivery of planned commercial oil volumes;
• for the first time by nanodemulsifier was realized cleaning waste water from the oil at this field to the level of Maximum Allowable Concentration (MAC, 50 mg/l) in oil preparation conditions, without the use of special equipment and technology training produced water to maintain reservoir pressure;
• nanodemulsifier "IKHLAS"-1, in contrast to the analogues, displayed also function of mixture HDWOE with HDWOS.
• Demulsification processes of persistent oil emulsions are additionally hampered also
by the presence of solid inorganic nanopar-ticles, for example clay and iron sulfide, in the compositions of structural-mechanical adsorption barriers (SMAB). There is no doubt, that energy adsorption of nanoparti-cles is much higher than the energy of adsorption of surfactant molecules. Therefore, for most basic demulsifiers there exist problems in primary preparation of stable emulsions. Consequently, the demulsifier should provide competition against the adsorption of nanoparticles. Therefore, we have developed special functional nano-structured demulsifiers (FND) for dehydration and desalting HDWOE, for which the interfacial tension reaches zero. For effective FND their surface activity is much higher than the surface activity of the components of SMAB, including the inorganic nanoparticles.
• In conformity with the results of the EIT the conclusion has been drawn that "IKHLAS"-1 compared to the basic demulsifier "Randem" 2219 possesses significant technological, environmental and economic advantages. Therefore, we consider it appropriate to recommend the nanodemulsifier "IKHLAS"-1 (with an optimum dose of ~160 g/t) for the widespread introduction at the SPPO "Zhetybay", and in other similar oil-fields
where there is a problem in primary preparation stable oil emulsions. • Thus, the development and implementation of nanodeemulgator for demulsification of oil, is one of priority directions of modern oil-field chemistry.
References
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NEFT EMULSiYALARININ DEEMULSASiYASI ÛÇÛN NANODEEMULQATORLARIN TOTBiQi MÜASiR NEFT-MODON KiMYASININ PRiORiTET iSTiQAMOTLORiNDON BiRlDiR
T.K.Da$diyeva
Maqalada "IKHLAS"-1-42 (yüksak va açagi molekul kütlali SFM-lar asasinda) nanodeemulqator kompozisiyalannin Qazaxstan Respublikasinin "Jetibay" va "Janaozen" yataqlarinda aparilan laboratoriya va tacrüba-sanaye sinaq naticalari verilir. Sanaye sinaq naticalarina istinadan bela natica alda edilmiçdir ki, "IKHLAS"-1, "Randem" 2219 deemulqatoru ila müqayisada yüksak texnoloji, ekoloji va iqtisadi üstünlüklara malik olmuçdur. Ona göra da "IKHLAS"-1 nanodeemulqatorunun "Jetibaymunaygaz" yataginda geniç miqyasda tatbiq edilmasi ila yanaçi, neftin ilkin hazirlanmasi zamam davamli neft emulsiyalari ila bagli problemlar yaçanan digar analoji neft yataqlarinda da tatbiq edilmasi tarafimizdan taklif edilmiçdir.
Açar sözlar: neft-msdsn kimyasi, çstin parçalanan neft-su emulsiyalari, nanodeemulqatorlar, desuspenzatorlar, nano-hissacikhr, qeyrri-ionogen ssthi-ßal maddshr.
ПРИМЕНЕНИЕ НАНОДЕЭМУЛЬГАТОРОВ ДЛЯ ДЕЭМУЛЬСАЦИИ НЕФТЯНЫХ ЭМУЛЬСИЙ ЯВЛЯЕТСЯ ОДНИМ ИЗ ПРИОРИТЕТНЫХ НАПРАВЛЕНИЙ СОВРЕМЕННОЙ НЕФТЕПРОМЫСЛОВОЙ ХИМИИ
Т.К.Дашдиева
Приведены результаты лабораторных и опытно-промышленных испытаний композиций нанодеэмульгаторов "IKHLAS"-1-42 (на основе высокомолекулярных и низкомолекулярных ПАВ) на месторождениях "Жетыбай", "Жанаозен" Республики Казахстан. По результатам опытно-промышленных испытаний, сделан вывод о том, что IKHLAS-1 по сравнению с базовым деэмульгатором "Рандем" 2219 обладает значительными технологическими, экологическими и экономическими преимуществами. Поэтому нанодеэмульгатор "IKHLAS"-1 рекомендован нами (с оптимальной дозой ~160 г/т) для широкого внедрения на месторождении " Жетыбаймунайгаз", а также на других аналогичных нефтяных месторождениях, в которых имеются проблемы при первичной подготовке стойких нефтяных эмульсий.
Ключевые слова: нефтепромысловая химия, трудноразрушаемые водо-нефтяные эмульсии, нанодеэмульгато-ры, десуспензаторы, наночастицы, неионогенные поверхностно-активные вещества.
