RU2671198C1 - Inhibitor of asphalt and resin paraffin deposits for paraffinous and highly paraffinous oils - Google Patents
Inhibitor of asphalt and resin paraffin deposits for paraffinous and highly paraffinous oils Download PDFInfo
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- RU2671198C1 RU2671198C1 RU2018124542A RU2018124542A RU2671198C1 RU 2671198 C1 RU2671198 C1 RU 2671198C1 RU 2018124542 A RU2018124542 A RU 2018124542A RU 2018124542 A RU2018124542 A RU 2018124542A RU 2671198 C1 RU2671198 C1 RU 2671198C1
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- paraffinous
- inhibitor
- asphalt
- resin
- oils
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- 239000003112 inhibitor Substances 0.000 title claims abstract description 16
- 229920005989 resin Polymers 0.000 title claims abstract description 8
- 239000011347 resin Substances 0.000 title claims abstract description 8
- 239000012188 paraffin wax Substances 0.000 title abstract description 16
- 239000010426 asphalt Substances 0.000 title abstract 2
- 239000003921 oil Substances 0.000 title description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003208 petroleum Substances 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- HUQJFYXIIIYJCX-UHFFFAOYSA-N dodecan-1-amine;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCCCCCCCCN HUQJFYXIIIYJCX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002641 tar oil Substances 0.000 claims abstract 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 229920000800 acrylic rubber Polymers 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 239000010690 paraffinic oil Substances 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000002952 polymeric resin Substances 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- GTGUCSIFKYFMNY-UHFFFAOYSA-N dodecylazanium;hydrogen sulfate Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCN GTGUCSIFKYFMNY-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000000540 fraction c Anatomy 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
-
- 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
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B37/00—Methods or apparatus for cleaning boreholes or wells
- E21B37/06—Methods or apparatus for cleaning boreholes or wells using chemical means for preventing or limiting, e.g. eliminating, the deposition of paraffins or like substances
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Fluid Mechanics (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
Изобретение относится к области ингибирования процесса образования нежелательных отложений в нефтепромысловом оборудовании и может быть использовано при транспортировке и хранении нефти.The invention relates to the field of inhibition of the process of formation of unwanted deposits in oilfield equipment and can be used in transportation and storage of oil.
Известен ингибитор асфальтосмолопарафиновых отложений [US 6750305 В2, МПК C08F 26/08, опубл. 15.06.2004], который был получен на основе полимера А, состоящего из: 73 мас. % акрилатов С18-С22; 15 мас. % акрилатов С30; а также 12 мас. % N-винилпирролидона.A known inhibitor of asphalt-resin-paraffin deposits [US 6750305 B2, IPC C08F 26/08, publ. 06/15/2004], which was obtained on the basis of polymer A, consisting of: 73 wt. % acrylates C 18 -C 22 ; 15 wt. % acrylates C 30 ; as well as 12 wt. % N-vinylpyrrolidone.
Известен состав ингибитора асфальтосмолопарафиновых отложений [RU 2480505 С1, МПК С09K 8/524 (2006.01), опубл. 27.04.2013], включающий в себя реагент 1 и реагент 2 при их массовом соотношении 33,4% к 66,6%. При изготовлении реагента 1 применяется только стеариновая кислота и полиэтиленполиамины, а для изготовления реагента 2 - стеариновая кислота и пентаэритрит. Реагент 1 является продуктом синтеза стеариновой кислоты и полиэтиленполиаминов при их мольном соотношении 1,63 к 1. Реагент 2 является продуктом синтеза стеариновой кислоты и пентаэритрита при мольном их соотношении 3 к 1.The known composition of the inhibitor of asphalt-resin-paraffin deposits [RU 2480505 C1, IPC C09K 8/524 (2006.01), publ. 04/27/2013], which includes reagent 1 and reagent 2 with their mass ratio of 33.4% to 66.6%. In the manufacture of reagent 1, only stearic acid and polyethylene polyamines are used, and for the manufacture of reagent 2, stearic acid and pentaerythritol are used. Reagent 1 is the product of the synthesis of stearic acid and polyethylene polyamines in their molar ratio of 1.63 to 1. Reagent 2 is the product of the synthesis of stearic acid and pentaerythritol in their molar ratio of 3 to 1.
Известен ингибитор на основе сополимеров, содержащих этилен, виниловые сложные эфиры, в частности винилацетат и сложные эфиры (мет)акриловой кислоты, полученные из сложных эфиров, содержащих разветвленные алкильные, циклические алкильные или алкилзамещенные арильные фрагменты и имеющие среднюю молекулярную массу от 35000 г/моль до 150000 г/моль [СА 2889070 С, МПК C08F 2/06, опубл. 28.11.2017].Known inhibitor based on copolymers containing ethylene, vinyl esters, in particular vinyl acetate and esters of (meth) acrylic acid, obtained from esters containing branched alkyl, cyclic alkyl or alkyl substituted aryl fragments and having an average molecular weight of 35,000 g / mol up to 150,000 g / mol [CA 2889070 C, IPC C08F 2/06, publ. 11/28/2017].
Однако вышеперечисленные ингибиторы отличаются сложной технологией производства и низкой степенью ингибирования процесса образования асфальтосмолопарафиновых отложений для парафинистых и высокопарафинистых смолистых нефтей.However, the above inhibitors are distinguished by a complex production technology and a low degree of inhibition of the formation of asphalt-resin-paraffin deposits for paraffinic and highly paraffinic resinous oils.
Известен ингибитор асфальтосмолопарафиновых отложений (присадка К-210) [RU 2541680, МПК (2006.01) С09К 8/524, опубл. 20.02.2015.], выбранный в качестве прототипа и имеющий следующий состав, мас. %:Known inhibitor of asphalt-resin-paraffin deposits (additive K-210) [RU 2541680, IPC (2006.01) C09K 8/524, publ. 02/20/2015.], Selected as a prototype and having the following composition, wt. %:
Однако он недостаточно эффективен для нефтей с массовой долей парафиновых углеводородов более 10% мас., смолисто-асфальтеновых компонентов более 20% мас. и для перекачки нефти и нефтепродуктов при температурах ниже 20°С.However, it is not effective enough for oils with a mass fraction of paraffin hydrocarbons of more than 10% wt., Resinous-asphaltene components of more than 20% wt. and for pumping oil and oil products at temperatures below 20 ° C.
Техническим результатом предложенного изобретения является разработка состава ингибитора, обладающего высокой степенью ингибирования процесса образования асфальтосмолопарафиновых отложений в парафинистых и высокопарафинистых смолистых нефтях. Ингибитор асфальтосмолопарафиновых отложений для парафинистых и высокопарафинистых смолистых нефтей, также как в прототипе, содержит сополимер алкилакрилатов С16-С20 с акрилатом додециламина и толуол.The technical result of the proposed invention is the development of an inhibitor composition having a high degree of inhibition of the formation of asphalt-resin-paraffin deposits in paraffinic and high-paraffin resinous oils. Inhibitor of asphalt-resin-paraffin deposits for paraffinic and high-paraffin resinous oils, as in the prototype, contains a copolymer of C 16 -C 20 alkyl acrylates with dodecylamine acrylate and toluene.
Согласно изобретению ингибитор дополнительно содержит окисленную нефтеполимерную смолу при следующем соотношении компонентов, мас. %:According to the invention, the inhibitor further comprises an oxidized petroleum polymer resin in the following ratio of components, wt. %:
Окисленную нефтеполимерную смолу получают окислением нефтеполимерной смолы, синтезированной термической полимеризацией непредельных соединений фракции С9 жидких продуктов пиролиза, 9% Н2О2 по методике, приведенной в [Fisenko D.V., Manankova А.А, Bondaletov V.G., Fillipova M.Y., Yakimova V.A. Oxidative modification of petroleum resins and reception of emulsions with industrial oils // Petroleum and Coal. 2016. V. 58. №5. P. 590-596]The oxidized petroleum polymer resin is obtained by oxidizing an oil polymer resin synthesized by thermal polymerization of unsaturated compounds of fraction C 9 of liquid pyrolysis products, 9% H 2 O 2 according to the procedure described in [Fisenko DV, Manankova A.A., Bondaletov VG, Fillipova MY, Yakimova VA Oxidative modification of petroleum resins and reception of emulsions with industrial oils // Petroleum and Coal. 2016. V. 58. No. 5. P. 590-596]
В таблице 1 представлены рецептуры получения предлагаемых ингибиторов.Table 1 presents the formulation of the proposed inhibitors.
В таблице 2 показана степень ингибирования асфальтосмолопарафиновых отложений в парафинистых и высокопарафинистых смолистых нефтях в зависимости от состава предлагаемых ингибиторов.Table 2 shows the degree of inhibition of asphalt-resin-paraffin deposits in paraffinic and high-paraffin resinous oils, depending on the composition of the proposed inhibitors.
Ингибитор-1 получили путем смешения растворов реагента 1 и реагента 2 при их массовом соотношении 95,0% к 5,0%. Реагент 1 готовили растворением 49,5 г сополимера алкилакрилатов С16-С20 с акрилатом додециламином в 50,5 г (58,3 см3) толуола. Реагент 2 получали растворением 30,0 г окисленных нефтеполимерных смол в 70 г (79,5 cm3) о-ксилола. Рецептура получения других ингибиторов представлена в таблице 1.Inhibitor-1 was obtained by mixing solutions of reagent 1 and reagent 2 with a mass ratio of 95.0% to 5.0%. Reagent 1 was prepared by dissolving 49.5 g of a copolymer of alkyl C 16 -C 20 acrylate in 50.5 g of dodecylamine (58.3 cm3) of toluene. Reagent 2 was prepared by dissolving 30.0 g of oxidized petroleum polymer resins in 70 g (79.5 cm 3 ) of o-xylene. The formulation of other inhibitors is presented in table 1.
Количественную оценку процесса осадкообразования определяли на установке, разработанной на основе известного метода «холодного стержня» [Агаев С.Г., Березина З.Н., Халин А.А. // Нефтепромысловое дело. 1996. №5. С. 16].A quantitative assessment of the process of precipitation was determined on the installation developed on the basis of the well-known method of the "cold rod" [Agaev SG, Berezina Z.N., Halin A.A. // Oilfield business. 1996. No5. S. 16].
Степень ингибирования процесса осадкообразования рассчитывали по формуле:The degree of inhibition of the precipitation process was calculated by the formula:
где I - степень ингибирования, %;where I is the degree of inhibition,%;
min - масса осадка исходной образца, г;m in is the mass of sediment of the initial sample, g;
mобр - масса осадка образца в присутствии присадки, г.m arr is the mass of sediment in the presence of an additive, g
Степень ингибирования асфальтосмолопарафиновых отложений всеми исследуемыми ингибиторами, взятыми в концентрации 0,03-0,05 мас. %, оценивали для парафинистых, высокопарафинистых смолистых нефтей.The degree of inhibition of asphalt-resin-paraffin deposits by all investigated inhibitors, taken at a concentration of 0.03-0.05 wt. %, evaluated for paraffinic, highly paraffinic resinous oils.
Анализ результатов, представленных в таблице 2, показывает, что предлагаемый ингибитор имеет более высокую степень ингибирования по сравнению с прототипом (присадкой К-210) для парафинистых и высокопарафинистых смолистых нефтей.Analysis of the results presented in table 2 shows that the proposed inhibitor has a higher degree of inhibition compared to the prototype (additive K-210) for paraffinic and highly paraffin resinous oils.
ПУ - парафиновые углеводороды.PU - paraffin hydrocarbons.
САК - смолисто-асфальтеновые компоненты.NAO - tarry and asphaltene components.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2018124542A RU2671198C1 (en) | 2018-07-04 | 2018-07-04 | Inhibitor of asphalt and resin paraffin deposits for paraffinous and highly paraffinous oils |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2018124542A RU2671198C1 (en) | 2018-07-04 | 2018-07-04 | Inhibitor of asphalt and resin paraffin deposits for paraffinous and highly paraffinous oils |
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| RU2671198C1 true RU2671198C1 (en) | 2018-10-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2804193C1 (en) * | 2022-11-01 | 2023-09-26 | федеральное государственное бюджетное образовательное учреждение высшего образования "Югорский государственный университет" | Inhibitor additive for paraffinic and highly paraffinic resinous oils |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1102900A1 (en) * | 1983-03-21 | 1984-07-15 | Сибирский научно-исследовательский институт нефтяной промышленности | Method of preventing formation of paraffin deposits in oil-field equipment |
| WO1998021446A1 (en) * | 1996-11-14 | 1998-05-22 | Bp Exploration Operating Company Limited | Inhibitors and their uses in oils |
| RU2249674C1 (en) * | 2003-12-22 | 2005-04-10 | Институт химии нефти СО РАН (ИХН СО РАН) | Composition for inhibition of asphalt-resin-paraffin precipitations |
| RU2541680C1 (en) * | 2014-03-21 | 2015-02-20 | Общество с ограниченной ответственностью "Научно-производственное предприятие КВАЛИТЕТ" (ООО "НПП КВАЛИТЕТ") | Inhibitor of asphaltresinparaffin sediments |
| CN107325800A (en) * | 2016-04-28 | 2017-11-07 | 中国石油化工股份有限公司 | De-plugging and the stifled method of suppression and organic compounds containing nitrogen press down application of the blocking agent in thickened oil recovery as de-plugging in thickened oil recovery |
| US20180155608A1 (en) * | 2016-04-19 | 2018-06-07 | Halliburton Energy Services, Inc. | Double-headed hydrate inhibitors and methods of use |
-
2018
- 2018-07-04 RU RU2018124542A patent/RU2671198C1/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1102900A1 (en) * | 1983-03-21 | 1984-07-15 | Сибирский научно-исследовательский институт нефтяной промышленности | Method of preventing formation of paraffin deposits in oil-field equipment |
| WO1998021446A1 (en) * | 1996-11-14 | 1998-05-22 | Bp Exploration Operating Company Limited | Inhibitors and their uses in oils |
| RU2249674C1 (en) * | 2003-12-22 | 2005-04-10 | Институт химии нефти СО РАН (ИХН СО РАН) | Composition for inhibition of asphalt-resin-paraffin precipitations |
| RU2541680C1 (en) * | 2014-03-21 | 2015-02-20 | Общество с ограниченной ответственностью "Научно-производственное предприятие КВАЛИТЕТ" (ООО "НПП КВАЛИТЕТ") | Inhibitor of asphaltresinparaffin sediments |
| US20180155608A1 (en) * | 2016-04-19 | 2018-06-07 | Halliburton Energy Services, Inc. | Double-headed hydrate inhibitors and methods of use |
| CN107325800A (en) * | 2016-04-28 | 2017-11-07 | 中国石油化工股份有限公司 | De-plugging and the stifled method of suppression and organic compounds containing nitrogen press down application of the blocking agent in thickened oil recovery as de-plugging in thickened oil recovery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2804193C1 (en) * | 2022-11-01 | 2023-09-26 | федеральное государственное бюджетное образовательное учреждение высшего образования "Югорский государственный университет" | Inhibitor additive for paraffinic and highly paraffinic resinous oils |
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