RU2680522C1 - Method for regenerative cleaning of hydrocarbon raw from acid impurities - Google Patents
Method for regenerative cleaning of hydrocarbon raw from acid impurities Download PDFInfo
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- RU2680522C1 RU2680522C1 RU2018116500A RU2018116500A RU2680522C1 RU 2680522 C1 RU2680522 C1 RU 2680522C1 RU 2018116500 A RU2018116500 A RU 2018116500A RU 2018116500 A RU2018116500 A RU 2018116500A RU 2680522 C1 RU2680522 C1 RU 2680522C1
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- Prior art keywords
- organic acids
- alkaline
- acidic impurities
- concentrate
- alkaline solution
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000012535 impurity Substances 0.000 title claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 11
- 238000004140 cleaning Methods 0.000 title abstract description 5
- 239000002253 acid Substances 0.000 title description 3
- 230000001172 regenerating effect Effects 0.000 title 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 30
- 150000007524 organic acids Chemical class 0.000 claims abstract description 16
- 235000005985 organic acids Nutrition 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 239000012670 alkaline solution Substances 0.000 claims abstract description 14
- 239000012141 concentrate Substances 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 9
- 159000000001 potassium salts Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000003350 kerosene Substances 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 238000007670 refining Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000005608 naphthenic acid group Chemical group 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 102200118166 rs16951438 Human genes 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
-
- 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
-
- 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/08—Recovery of used refining agents
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
Изобретение относится к способам очистки углеводородного сырья (бензиновых, керосиновых, дизельных фракций, легких нефтей, газоконденсатов и т.п.) от кислых примесей и который может быть использовано в нефтеперерабатывающей, нефтедобывающей и нефтехимической отраслях промышленности.The invention relates to methods for cleaning hydrocarbon feedstocks (gasoline, kerosene, diesel fractions, light oils, gas condensates, etc.) from acidic impurities and which can be used in the oil refining, oil producing and petrochemical industries.
Кислотность нефти и нефтепродуктов зависит от содержания в них нафтеновых, карбоновых и оксикарбоновых кислот, фенолов и других соединений кислотного характера, которые влияют на коррозию оборудования и двигателей. Из перечисленных соединений нафтеновые кислоты играют доминирующую роль [1].The acidity of oil and petroleum products depends on the content of naphthenic, carboxylic and hydroxycarboxylic acids, phenols and other acid compounds in them, which affect the corrosion of equipment and engines. Of these compounds, naphthenic acids play a dominant role [1].
Известны методы очистки углеводородных дистиллятов - бензиновой, керосиновой, дизельной фракций от кислых примесей (сероводорода, алифатических, ароматичесих и нафтеновых кислот, фенолов) 1÷7% водными растворами гидроксида натрия или калия [2-4].Known methods for the purification of hydrocarbon distillates - gasoline, kerosene, diesel fractions from acidic impurities (hydrogen sulfide, aliphatic, aromatic and naphthenic acids, phenols) 1 ÷ 7% aqueous solutions of sodium or potassium hydroxide [2-4].
Недостатком этих способов является непрерывное образование токсичных сернисто-щелочных стоков, содержащих соли органических кислот, что приводит к необходимости последующей стадии их обезвреживания и утилизации одним из известных способов.The disadvantage of these methods is the continuous formation of toxic sulfur-alkaline effluents containing salts of organic acids, which leads to the need for a subsequent stage of neutralization and disposal of one of the known methods.
По технической сущности и достигаемому результату наиболее близким к предлагаемому является способ очистки углеводородного сырья от кислых примесей [1] извлечением органических кислот 1-7% водными растворами гидроксида натрия.According to the technical nature and the achieved result, the closest to the proposed one is a method of purification of hydrocarbon raw materials from acidic impurities [1] by extracting organic acids with 1-7% aqueous solutions of sodium hydroxide.
Недостатком способа [1] является образование сернисто-щелочных стоков, содержащих соли органических кислот, и необходимость их последующего обезвреживания и утилизации.The disadvantage of this method [1] is the formation of sulfur-alkaline effluents containing salts of organic acids, and the need for their subsequent neutralization and disposal.
Задачей настоящего изобретения является устранение указанных недостатков. Согласно изобретения это достигается использованием для хемосорбции кислых примесей водного раствора гидроксида калия с концентрацией от 40 до 50% масс, позволяющего получать и выделять концентрат солей органических кислот в жидком виде для их последующей утилизации. При этом щелочной раствор после отстаивания и отделения от концентрата солей органических кислот используется повторно. Концентрация щелочного раствора поддерживается постоянной добавлением в него расчетного количества твердого гидроксида калия. Накапливаемая в щелочном растворе реакционная вода, выделяющаяся при поглощении кислых примесей по реакции 1, подвергается отдувке газом или отпарке.The objective of the present invention is to remedy these disadvantages. According to the invention, this is achieved by using for the chemisorption of acidic impurities an aqueous solution of potassium hydroxide with a concentration of from 40 to 50% by mass, which makes it possible to obtain and isolate a concentrate of salts of organic acids in liquid form for their subsequent disposal. In this case, the alkaline solution after settling and separation from the concentrate of salts of organic acids is reused. The concentration of the alkaline solution is maintained by the constant addition of a calculated amount of solid potassium hydroxide. The reaction water accumulated in an alkaline solution released during the absorption of acidic impurities by reaction 1 is subjected to gas stripping or stripping.
Отличительным признаком предлагаемого способа щелочной очистки углеводородных дистиллятов от кислых примесей является использование в качестве щелочного раствора 40-50%-ого раствора гидроксида калия, позволяющего осуществить регенерацию используемого щелочного раствора с одновременным получением концентрата калиевых солей органических кислот, востребованных в качестве моющих присадок и деэмульгаторов при обезвоживании нефти, и исключить образование на этой стадии токсичных сернисто-щелочных стоков, требующих их обезвреживания и утилизации.A distinctive feature of the proposed method for alkaline cleaning of hydrocarbon distillates from acidic impurities is the use of a 40-50% solution of potassium hydroxide as an alkaline solution, which allows the regeneration of the alkaline solution used while obtaining a concentrate of potassium salts of organic acids, which are in demand as detergents and demulsifiers with dehydration of oil, and to eliminate the formation of toxic sulfur-alkaline effluents at this stage, requiring their neutralization and tilizatsii.
Указанный отличительный признак определяет существенные отличия предложенного способа от прототипа и известного уровня техники в представленной области, т.к. предложенный способ очистки углеводородного сырья от кислых примесей водными растворами гидроксида калия с концентрацией 40-50% не описан в литературе и позволяет, по сравнению с прототипом, усовершенствовать технологию очистки углеводородов от кислых примесей, сократить эксплуатационные затраты за счет исключения необходимости обезвреживания и утилизации образующихся стоков, а также выделять в качестве побочного продукта очистки дистиллятов от кислых примесей концентрата калиевых солей органических кислот в жидком виде.The specified distinguishing feature determines the significant differences of the proposed method from the prototype and prior art in the presented field, because the proposed method for purification of hydrocarbon raw materials from acidic impurities with aqueous solutions of potassium hydroxide with a concentration of 40-50% is not described in the literature and allows, in comparison with the prototype, to improve the technology for purification of hydrocarbons from acidic impurities, reduce operating costs by eliminating the need for disposal and disposal of waste water and also isolate as a by-product of the purification of distillates from acidic impurities of the concentrate of potassium salts of organic acids in liquid form.
Предлагаемый способ апробирован в лабораторных условиях на бензиновой, керосиновой и дизельной фракциях. Ниже приведены примеры и результаты проведенных опытов.The proposed method is tested in laboratory conditions on gasoline, kerosene and diesel fractions. Below are examples and results of the experiments.
Пример 1.Example 1
Отстаивание и разделение концентрата солей органических кислот от щелочного раствора после его отделения от углеводородной фазы оценивали количественно. Кислотное число углеводородной фракции определяли по ГОСТ 5985-79. Эксперименты проводили при следующих условиях: объем углеводородной фракции 10000 мл, объем щелочного раствора - 50 мл, температура опытов 20°С, время перемешивания - 3 мин. Результаты испытаний приведены в табл. 1.The sedimentation and separation of the concentrate of salts of organic acids from the alkaline solution after its separation from the hydrocarbon phase was quantified. The acid number of the hydrocarbon fraction was determined according to GOST 5985-79. The experiments were carried out under the following conditions: the volume of the hydrocarbon fraction was 10,000 ml, the volume of the alkaline solution was 50 ml, the temperature of the experiments was 20 ° C, and the mixing time was 3 min. The test results are given in table. one.
Из приведенных в табл. 1 данных видно, что выделение концентрата калиевых солей органических кислот возможно исключительно при использовании щелочного раствора гидроксида калия с концентрацией 40-50% масс.From the above table. 1 data shows that the allocation of a concentrate of potassium salts of organic acids is possible only when using an alkaline solution of potassium hydroxide with a concentration of 40-50% of the mass.
Таким образом, предлагаемый способ очистки углеводородного сырья от кислых примесей исключает образование токсичных щелочных стоков, содержащих соли органических кислот, позволяет выделять в качестве побочного продукта концентрат калиевых солей органических кислот, то есть сократить эксплуатационные затраты на реализацию этих процессов по сравнению с известным способом по прототипу.Thus, the proposed method of purification of hydrocarbon raw materials from acidic impurities eliminates the formation of toxic alkaline effluents containing salts of organic acids, allows you to allocate a concentrate of potassium salts of organic acids as a by-product, that is, to reduce operating costs for the implementation of these processes in comparison with the known method of the prototype .
ЛитератураLiterature
1. Технический анализ нефтепродуктов и газа. Белянин Б.В., Эрих В.Н. Л.: Химия, 1979, - 224 с.1. Technical analysis of oil products and gas. Belyanin B.V., Erich V.N. L .: Chemistry, 1979, - 224 p.
2. Ситтиг М. Процессы окисления углеводородного сырья. - М.: Химия, 1970. - 300 с.2. Sittig M. Processes for the oxidation of hydrocarbons. - M.: Chemistry, 1970 .-- 300 p.
3. Мейерс Р.А. Основные процессы нефтепереработки. Справочник. Изд. ЦОП «Профессия», Санкт-Петербург, 2012 г., 944 с.3. Meyers R.A. The main processes of oil refining. Directory. Ed. CCP “Profession”, St. Petersburg, 2012, 944 p.
4. Пат. РФ 2087521, C10G 27/10,1997 г.4. Pat. RF 2087521, C10G 27/10/1997
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2018116500A RU2680522C1 (en) | 2018-05-03 | 2018-05-03 | Method for regenerative cleaning of hydrocarbon raw from acid impurities |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2018116500A RU2680522C1 (en) | 2018-05-03 | 2018-05-03 | Method for regenerative cleaning of hydrocarbon raw from acid impurities |
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| RU2680522C1 true RU2680522C1 (en) | 2019-02-22 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4252637A (en) * | 1978-04-27 | 1981-02-24 | Deutsche Gold Und Silber-Scheideanstalt Vormals Roessler | Process for the reprocessing of used lubricating oils (II) |
| WO1993025636A1 (en) * | 1992-06-08 | 1993-12-23 | Hja-Engineering Oy | Method for desulfurization of liquid fuels and petrochemical feedstocks |
| RU2145972C1 (en) * | 1998-05-25 | 2000-02-27 | Ахмадуллина Альфия Гариповна | Method of cleaning high-boiling hydrocarbon fractions from mercaptans and acid impurities |
| RU2283856C2 (en) * | 2003-12-19 | 2006-09-20 | Ахматфаиль Магсумович Фахриев | Hydrogen sulfide containing crude oil treatment process |
| RU2436620C1 (en) * | 2010-07-01 | 2011-12-20 | Ахмед Ибрагим Шакер Салех | Method to treat hydrocarbon products from acid admixtures |
-
2018
- 2018-05-03 RU RU2018116500A patent/RU2680522C1/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4252637A (en) * | 1978-04-27 | 1981-02-24 | Deutsche Gold Und Silber-Scheideanstalt Vormals Roessler | Process for the reprocessing of used lubricating oils (II) |
| WO1993025636A1 (en) * | 1992-06-08 | 1993-12-23 | Hja-Engineering Oy | Method for desulfurization of liquid fuels and petrochemical feedstocks |
| RU2145972C1 (en) * | 1998-05-25 | 2000-02-27 | Ахмадуллина Альфия Гариповна | Method of cleaning high-boiling hydrocarbon fractions from mercaptans and acid impurities |
| RU2283856C2 (en) * | 2003-12-19 | 2006-09-20 | Ахматфаиль Магсумович Фахриев | Hydrogen sulfide containing crude oil treatment process |
| RU2436620C1 (en) * | 2010-07-01 | 2011-12-20 | Ахмед Ибрагим Шакер Салех | Method to treat hydrocarbon products from acid admixtures |
Non-Patent Citations (1)
| Title |
|---|
| БЕЛЯНИН Б.В., ЭРИХ В.Н. ТЕХНИЧЕСКИЙ АНАЛИЗ НЕФТЕПРОДУКТОВ И ГАЗА. - Л.: ХИМИЯ, 1979. * |
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