WO2010136843A2 - Method for removing mercaptans from crude oil and petroleum distillates by oxidation - Google Patents
Method for removing mercaptans from crude oil and petroleum distillates by oxidation Download PDFInfo
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- WO2010136843A2 WO2010136843A2 PCT/IB2009/006516 IB2009006516W WO2010136843A2 WO 2010136843 A2 WO2010136843 A2 WO 2010136843A2 IB 2009006516 W IB2009006516 W IB 2009006516W WO 2010136843 A2 WO2010136843 A2 WO 2010136843A2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
Definitions
- the invention relates to the oxidative purification of oil and oil distillates, in particular heating oil, from mercaptans and hydrogen sulfide and can be used in the oil refining industry.
- the main disadvantages of this method are the insufficiently high degree of oxidation of mercaptans in oil and petroleum distillates, the low stability of the catalyst and the high energy intensity of the process.
- the closest to the described method in terms of technical nature and the achieved result is a method of oxidative demercaptanization of oil and oil distillates in the presence of a heterogeneous catalyst based on transition metal oxides of groups Ib, V-VIIb of the Periodic table or oxides of Ni or Co and nitrogen-containing organic compounds.
- the process is carried out at a temperature of 10 - 80 0 C, pressure 1 -10 atm. in the presence of air or oxygen or an oxygen-containing gas containing at least 5 ° / L oxygen.
- the main disadvantages of this method are the low degree of oxidation of sulfur-containing compounds in oil and petroleum distillates, caused by the low stability of the catalyst.
- the technical result is to obtain high-purity oil and oil distillates due to more complete oxidation of sulfur-containing compounds and increase the stability of the catalytic system while reducing the cost of the process.
- the technical result is achieved in that as a catalyst using a mixture of a derivative of a transition metal bound to a complex with a nitrogen-containing ligand and triazines at a ratio of a complex of a transition metal derivative / triazines 1 / 3.0
- a nitrogen-air mixture with an oxygen content of at least 3% by volume is used as an oxidizing agent.
- Nickel and cobalt chlorides, copper and nickel acetates, copper and cobalt naphthenates, copper (II) oxychloride are used as a transition metal derivative.
- Amines for example methylamine, ethylamine, isopropylamine, triethylamine and other aliphatic amines, are used as nitrogen-containing compounds.
- Distinctive features of the proposed method are the use of a mixture of a homogeneous catalyst based on a transition metal compound, and in particular, nickel (ll), cobalt (ll) or copper (I 1 II) in combination with aliphatic amines and triazines with a mixture ratio of 1/3 - 1/4.
- Another distinguishing feature of the proposed method is the process in a slightly acidic environment.
- the invention can be implemented as follows.
- a catalyst is obtained.
- water-monoethanolamine in a ratio of 20/80% vol., in the specified mixture is dissolved calculated amounts of a transition metal derivative, for example cobalt naphthenate, and an aliphatic amine, for example tributylamine, in a ratio of 1/1 - 1/3, and the homogeneous catalyst thus obtained is kept further at a temperature of 80 - 95 0 C for 1-1, 2 hours. and air is passed through the catalyst solution.
- the calculated amount of triazine is added to the catalyst solution with stirring.
- a model fuel oil containing hydrogen sulfide and a calculated amount of a catalytic system is loaded into a batch reactor with a stirrer and the system is acidified to pH 5.5-6.0.
- the process of cleaning fuel oil from sulfur-containing compounds is carried out with stirring in the temperature range of 20 - 120 0 C for 0.1-0.5 hours.
- a nitrogen-air mixture with an oxygen content of at least 3% by volume is fed into the reactor.
- fuel oil is unloaded and analyzed for the content of hydrogen sulfide.
- the method can be carried out in continuous mode.
- a mixture of a catalyst and a triazine is periodically or continuously introduced into a fuel oil stream flowing through a flow reactor equipped with a temperature control system, and at the same time it is blown through the reactor, or a nitrogen-air mixture is supplied together with fuel oil.
- a nitrogen-air mixture is supplied together with fuel oil.
- catalytic systems based on other compounds of the above transition metals, aliphatic amines and triazines are prepared as in the above example, except that they change the ratio of components.
- the composition and ratio of components of the prepared catalyst systems in accordance with the present invention are shown in Table 1.
- Fuel oil content of fuel grades M-40 and M-100 is allowed sulfur content (in terms of elementary) 2.0% in May. for sulfur fuel oil and 3.5% in May. for sour fuel oils, including not more than 2 * 10 h % in May. hydrogen sulfide, therefore, model fuel oils were prepared with a content of sulfur compounds (mercaptans, etc.) of at least 3.5% in May, including hydrogen sulfide of at least 0.01% in May.
- Demerkaptization of model fuel oils is carried out in a 1-liter batch reactor of stainless steel with a steam jacket equipped with a mechanical stirrer, a thermometer and an air inlet and outlet system.
- a steam jacket equipped with a mechanical stirrer, a thermometer and an air inlet and outlet system.
- the reactor load 800 ml of the prepared model fuel oil and 3 ml of the catalytic system according to p.
- Example 1 (copper-ethanolamine-triazine oxychloride), acidify the system to pH 6.0, turn on a stirrer (60 rpm), pass through a reactor a nitrogen-air mixture (6 volumes of nitrogen - 1 volume of air), heat the fuel oil to a temperature of 100 0 C and incubated at this temperature for 10 minutes Then the reactor is cooled, the model fuel oil is unloaded, sedimented and the content of hydrogen sulfide is determined. According to the results of the analysis, the content of hydrogen sulfide in fuel oil after catalytic demercaptanization is 2.0 - 10% in May.
- the demercaptanization of model fuel oil is carried out as in Example 1, except that a catalyst based on copper (II) oxychloride and ethanolamine without the addition of triazine is used as a catalytic system.
- the content of hydrogen sulfide in fuel oil after catalytic demercaptanization is 2.0 “10 3 % in May.
- the demercaptanization of model fuel oil is carried out as in Example 1, except that the process parameters, the content and composition of the catalytic system are changed.
- the process parameters, the content and composition of the catalytic system, as well as the results of the demekaptization of fuel oil are presented in Table 2.
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Abstract
The invention relates to the purification by oxidation of crude oil and petroleum distillates, in particular heating fuel, in order to remove mercaptans and hydrogen sulfide, and can be used in the oil refining industry. A method is proposed for the catalytic removal of mercaptans from crude oil and petroleum distillates using the oxygen contained in air in the presence of a catalyst mixture containing a transition metal derivative bonded into a complex with a nitrogen-containing ligand and triazines, wherein the ratio between the transition metal derivative complex and the triazines ranges from 1/3.0 to 1/4.0, and the process is carried out in a reaction medium having a pH of between 5.5 and 6.0 and at a temperature of between 20 and 120°C, while the oxidizer consists of a nitrogen-air mixture having an oxygen content of at least 3 vol. %. The method can be used for producing high-purity crude oil and petroleum distillates as a result of a more thorough oxidation of the sulfur-containing compounds and greater stability of the catalytic system, while simultaneously improving the cost-performance ratio of the process.
Description
ОПИСАНИЕ ИЗОБРЕТЕНИЯ DESCRIPTION OF THE INVENTION
СПОСОБ ОКИСЛИТЕЛЬНОЙ ДЕМЕРКАПТАНИЗАЦИИ НЕФТИ И НЕФТЯНЫХMETHOD FOR OXIDATIVE DEMERCAPTANIZATION OF OIL AND OIL
ДИСТИЛЛЯТОВ.Distillates.
МКИ С 10 G 27Ю4MKI S 10 G 27YU4
Изобретение относится к окислительной очистке нефти и нефтяных дистиллятов, в частности топочного мазута, от меркаптанов и сероводорода и может быть использовано в нефтеперерабатывающей промышленности.The invention relates to the oxidative purification of oil and oil distillates, in particular heating oil, from mercaptans and hydrogen sulfide and can be used in the oil refining industry.
Известны способы демеркаптанизации нефти и нефтяных дистиллятов путем окисления серосодержащих соединений кислородом воздуха в присутствии щелочи и гетерогенных катализаторов, содержащих соединения переходных металлов, нанесенных на твердые носители. [ 1 ,2 ]Known methods for demercaptanization of oil and oil distillates by oxidation of sulfur-containing compounds with atmospheric oxygen in the presence of alkali and heterogeneous catalysts containing transition metal compounds supported on solid carriers. [ 12 ]
Основным недостатком указанных технических решений является низкая степень окисления серосодержащих соединений в нефти и нефтяных дистиллятах, значительные расходы щелочи и технологическое несовершенство процесса, осуществляемого в две стадии.The main disadvantage of these technical solutions is the low degree of oxidation of sulfur-containing compounds in oil and oil distillates, significant alkali consumption and technological imperfection of the process carried out in two stages.
Известен также способ демеркаптанизации нефти и нефтяных дистиллятов путем каталитического окисления серосодержащих соединений редокси-системой, включающей ионы трехвалентного железа и гетерополикислоту, которая обеспечивает полное реокисление восстановленного иона двухвалентного железа до трехвалентного кислородом воздуха. [ 3 ]There is also known a method of demercaptanization of oil and oil distillates by catalytic oxidation of sulfur-containing compounds by a redoxy system including ferric ions and a heteropoly acid, which provides complete reoxidation of the reduced ferrous ion to ferric oxygen. [3]
Недостатком указанного способа является невысокая степень демеркаптанизации, и кроме того использование редокси-системы такого рода может привести к интенсивной коррозии технологического оборудования.The disadvantage of this method is the low degree of demercaptanization, and in addition, the use of a redoxy system of this kind can lead to intense corrosion of technological equipment.
Известен также способ демеркаптанизации нефти и нефтяных дистиллятов путем обработки их кислородом воздуха в присутствии
гетерогенного катализатора, в котором в качестве последнего используют водорастворимую неорганическую соль меди, железа, никеля или кобальта нанесенную на углеродный волокнистый материал, содержащий окислы кальция, магния, меди, марганца, железа, цинка и алюминия в количестве до 0,03 мае. и процесс проводят при температуре 80 - 2200C. [ 4 ]There is also a method of demercaptanization of oil and oil distillates by treating them with atmospheric oxygen in the presence of heterogeneous catalyst, in which the water-soluble inorganic salt of copper, iron, nickel or cobalt deposited on a carbon fiber material containing oxides of calcium, magnesium, copper, manganese, iron, zinc and aluminum in an amount up to 0.03 May is used as the latter. and the process is carried out at a temperature of 80 - 220 0 C. [4]
Основными недостатками этого способа являются недостаточно высокая степень окисления меркаптанов в нефти и нефтяных дистиллятах, низкая стабильность катализатора и большая энергоемкость процесса.The main disadvantages of this method are the insufficiently high degree of oxidation of mercaptans in oil and petroleum distillates, the low stability of the catalyst and the high energy intensity of the process.
Наиболее близким к описываемому способу по технической сущности и достигаемому результату является способ окислительной демеркаптанизации нефти и нефтяных дистиллятов в присутствии гетерогенного катализатора на основе оксидов переходных металлов групп Ib, V-VIIb Периодической таблицы или оксидов Ni или Со и азотсодержащих органических соединений. Процесс проводят при температуре 10 - 800C, давлении 1 -10 атм. в присутствии воздуха или кислорода или кислородсодержащего газа, содержащего не менее 5°/Ь кислорода. [ 5 ]The closest to the described method in terms of technical nature and the achieved result is a method of oxidative demercaptanization of oil and oil distillates in the presence of a heterogeneous catalyst based on transition metal oxides of groups Ib, V-VIIb of the Periodic table or oxides of Ni or Co and nitrogen-containing organic compounds. The process is carried out at a temperature of 10 - 80 0 C, pressure 1 -10 atm. in the presence of air or oxygen or an oxygen-containing gas containing at least 5 ° / L oxygen. [ 5 ]
Основными недостатками этого способа являются невысокая степень окисления серосодержащих соединений в нефти и нефтяных дистиллятах, вызванная низкой стабильностью катализатора.The main disadvantages of this method are the low degree of oxidation of sulfur-containing compounds in oil and petroleum distillates, caused by the low stability of the catalyst.
Техническим результатом, на достижение которого направлено создание данного изобретения, является получение высокочистой нефти и нефтяных дистиллятов за счет более полного окисления серосодержащих соединений и повышения стабильности каталитической системы при одновременном снижении себестоимости процесса.The technical result, the achievement of which the creation of this invention is directed, is to obtain high-purity oil and oil distillates due to more complete oxidation of sulfur-containing compounds and increase the stability of the catalytic system while reducing the cost of the process.
Поставленный технический результат достигается тем, что в качестве катализатора используют смесь производного переходного металла
связанного в комплекс с азотсодержащим лигандом и триазинами при соотношении комплекс производного переходного металла/триазины 1/3,0The technical result is achieved in that as a catalyst using a mixture of a derivative of a transition metal bound to a complex with a nitrogen-containing ligand and triazines at a ratio of a complex of a transition metal derivative / triazines 1 / 3.0
- 1/4,0 и процесс ведут при рН реакционной среды 5,5 - 6,0 и температуре 20- 1 / 4.0 and the process is carried out at a pH of the reaction medium of 5.5 - 6.0 and a temperature of 20
— 1200C и в качестве окислителя используют азотно-воздушную смесь с содержанием кислорода не менее 3 % объемных.- 120 0 C and a nitrogen-air mixture with an oxygen content of at least 3% by volume is used as an oxidizing agent.
В качестве производного переходного металла используют хлориды никеля и кобальта, ацетаты меди и никеля, нафтенаты меди и кобальта, оксихлорид меди (II).Nickel and cobalt chlorides, copper and nickel acetates, copper and cobalt naphthenates, copper (II) oxychloride are used as a transition metal derivative.
В качестве азотсодержащих соединений используют амины, например метиламин, этиламин, изопропиламин, триэтиламин и др. алифатические амины.Amines, for example methylamine, ethylamine, isopropylamine, triethylamine and other aliphatic amines, are used as nitrogen-containing compounds.
В качестве триазинов используют 1 ,2,3-тpиaзин, 1 ,2,4-тpиaзин, 1 ,3,5- триазин, или их смеси в различных сочетаниях.As triazines, 1, 2,3-thiazine, 1, 2,4-thiazine, 1, 3,5-triazine, or mixtures thereof in various combinations are used.
Отличительными признаками предлагаемого способа являются использование смеси гомогенного катализатора на основе соединения переходного металла, и в частности, никeля(ll), кoбaльтa(ll) или меди (I1 II) в комплексе с алифатическими аминами и триазинами при соотношении компонентов смеси 1/3 - 1/4. Еще одним отличительным признаком предлагаемого способа является проведение процесса в слабокислой среде.Distinctive features of the proposed method are the use of a mixture of a homogeneous catalyst based on a transition metal compound, and in particular, nickel (ll), cobalt (ll) or copper (I 1 II) in combination with aliphatic amines and triazines with a mixture ratio of 1/3 - 1/4. Another distinguishing feature of the proposed method is the process in a slightly acidic environment.
Указанные отличительные признаки позволяют проводить процесс демеркаптанизации нефти и нефтяных дистиллятов с более высокой степенью превращения серосодержащих соединений при существенном снижении затрат на очистку целевого продукта.These distinctive features allow the process of demercaptanization of oil and oil distillates with a higher degree of conversion of sulfur-containing compounds with a significant reduction in the cost of cleaning the target product.
Изобретение может быть осуществлено следующим образом.The invention can be implemented as follows.
Первоначально получают катализатор. Готовят смесь . вода- моноэтаноламин в соотношении 20/80 % об., в указанной смеси растворяют
расчетные количества производного переходного металла, например нафтената кобальта, и алифатического амина, например трибутиламина, в соотношении 1/1 — 1/3 и полученный таким образом гомогенный катализатор выдерживают далее при температуре 80 - 950C в течение 1-1 ,2 час. и при этом через раствор катализатора пропускают воздух. Далее к раствору катализатора при перемешивании добавляют расчетное количество триазина. В реактор периодического действия с мешалкой загружают модельный мазут, содержащий сероводород и расчетное количество каталитической системы и подкисляют систему до рН 5,5-6,0. Процесс очистки мазута от серосодержащих соединений ведут при перемешивании в температурном интервале 20 - 1200C в течение 0,1-0,5 часа. В процессе очистки в реактор подают азото-воздушную смесь с содержанием кислорода не менее 3% объемных. По окончании процесса очистки мазут выгружают и анализируют на содержание сероводорода. Способ может быть осуществлен и в непрерывном режиме. В поток мазута, протекающий через проточный реактор, оборудованный системой терморегулирования, периодически или непрерывно вводят смесь катализатора и триазина и при этом продувают через реактор, или подают совместно с мазутом азото-воздушную смесь. При прохождении системы мазут-катализатор-триазин-воздух через реактор происходит полное окисление серосодержащих соединений.Initially, a catalyst is obtained. Prepare the mixture. water-monoethanolamine in a ratio of 20/80% vol., in the specified mixture is dissolved calculated amounts of a transition metal derivative, for example cobalt naphthenate, and an aliphatic amine, for example tributylamine, in a ratio of 1/1 - 1/3, and the homogeneous catalyst thus obtained is kept further at a temperature of 80 - 95 0 C for 1-1, 2 hours. and air is passed through the catalyst solution. Next, the calculated amount of triazine is added to the catalyst solution with stirring. A model fuel oil containing hydrogen sulfide and a calculated amount of a catalytic system is loaded into a batch reactor with a stirrer and the system is acidified to pH 5.5-6.0. The process of cleaning fuel oil from sulfur-containing compounds is carried out with stirring in the temperature range of 20 - 120 0 C for 0.1-0.5 hours. During the cleaning process, a nitrogen-air mixture with an oxygen content of at least 3% by volume is fed into the reactor. At the end of the cleaning process, fuel oil is unloaded and analyzed for the content of hydrogen sulfide. The method can be carried out in continuous mode. A mixture of a catalyst and a triazine is periodically or continuously introduced into a fuel oil stream flowing through a flow reactor equipped with a temperature control system, and at the same time it is blown through the reactor, or a nitrogen-air mixture is supplied together with fuel oil. When the fuel oil-catalyst-triazine-air system passes through the reactor, the sulfur-containing compounds are completely oxidized.
Для лучшего понимания изобретение может быть проиллюстрировано, но не исчерпано следующими примерами его конкретного осуществления.For a better understanding, the invention can be illustrated, but not exhausted by the following examples of its specific implementation.
Пример 1.Example 1
А. Приготовление катализатора *.A. Preparation of the catalyst *.
В стеклянную трехгорлую круглодонную колбу емкостью 500 мл оборудованную механической мешалкой, термометром и боковым вводом газа
заливают 60 мл дистиллированной воды и 240 мл этаноламина, далее при перемешивании в водно-этаноламинной смеси последовательно растворяют 1 ,5 г оксихлорида меди (II) и 1 ,85 г этаноламина, включают продувку системы воздухом, нагревают раствор в колбе до температуры 700C и термостатируют при этой температуре в течение 15 мин. Далее к раствору катализатора добавляют 10,5 г триазина (смесь 1 ,2,3-, 1 ,2,4- и 1 ,3,5- триазинов) и затем полученную таким образом каталитическую систему охлаждают до комнатной температуры.In a 500 ml glass three-necked round-bottom flask equipped with a mechanical stirrer, thermometer and side gas inlet pour 60 ml of distilled water and 240 ml of ethanolamine, then, while stirring in a water-ethanolamine mixture, 1, 5 g of copper (II) oxychloride and 1, 85 g of ethanolamine are successively dissolved, the system is purged with air, the solution is heated in a flask to a temperature of 70 0 C and thermostat at this temperature for 15 minutes Then, 10.5 g of triazine (a mixture of 1, 2,3-, 1, 2,4- and 1, 3,5-triazines) are added to the catalyst solution, and then the catalyst system thus obtained is cooled to room temperature.
*Пpимeчaниe: каталитические системы на основе других соединений перечисленных выше переходных металлов, алифатических аминов и триазинов готовят как в вышеописанном примере за исключением того, что изменяют соотношение компонентов. Состав и соотношение компонентов приготовленных каталитических систем в соответствии с настоящим изобретением приведены в Таблице 1.* Note: catalytic systems based on other compounds of the above transition metals, aliphatic amines and triazines are prepared as in the above example, except that they change the ratio of components. The composition and ratio of components of the prepared catalyst systems in accordance with the present invention are shown in Table 1.
Б. Демеркаптанизация модельного мазута.B. Demercaptanization of model fuel oil.
В соответствии с ГОСТ 10585-99 (п. 4.4.) в мазутах топочных марок M-40 и M-100 допускается содержание серы (в пересчете на элементарную) 2,0 % мае. для сернистых мазутов и 3,5 % мае. для высокосернистых мазутов, в том числе не более 2* 10ч % мае. сероводорода, поэтому были приготовлены модельные мазуты с содержанием сернистых соединений (меркаптанов и др.) не менее 3,5 % мае, в том числе сероводорода не менее 0,01 % мае.In accordance with GOST 10585-99 (Clause 4.4.), Fuel oil content of fuel grades M-40 and M-100 is allowed sulfur content (in terms of elementary) 2.0% in May. for sulfur fuel oil and 3.5% in May. for sour fuel oils, including not more than 2 * 10 h % in May. hydrogen sulfide, therefore, model fuel oils were prepared with a content of sulfur compounds (mercaptans, etc.) of at least 3.5% in May, including hydrogen sulfide of at least 0.01% in May.
Демеркаптанизацию модельных мазутов проводят в реакторе периодического действия емкостью 1 л из нержавеющей стали с паровой рубашкой, снабженном механической мешалкой, термометром и системой ввода и вывода воздуха. В реактор загружают 800 мл приготовленного модельного мазута и 3 мл каталитической системы по п. «A» Примера 1
(оксихлорид меди-этаноламин-триазин), подкисляют систему до рН 6,0, включают мешалку (60 об/мин), пропускают через реактор азотно-воздушную смесь (6 объемов азота - 1 объем воздуха), нагревают мазут до температуры 1000C и выдерживают при этой температуре в течение 10 мин. Затем реактор охлаждают, выгружают модельный мазут, отстаивают и определяют содержание сероводорода. По результатам анализа содержание сероводорода в мазуте после каталитической демеркаптанизации составляет 2,0 - Ю^ Уо мае.Demerkaptization of model fuel oils is carried out in a 1-liter batch reactor of stainless steel with a steam jacket equipped with a mechanical stirrer, a thermometer and an air inlet and outlet system. In the reactor load 800 ml of the prepared model fuel oil and 3 ml of the catalytic system according to p. "A" of Example 1 (copper-ethanolamine-triazine oxychloride), acidify the system to pH 6.0, turn on a stirrer (60 rpm), pass through a reactor a nitrogen-air mixture (6 volumes of nitrogen - 1 volume of air), heat the fuel oil to a temperature of 100 0 C and incubated at this temperature for 10 minutes Then the reactor is cooled, the model fuel oil is unloaded, sedimented and the content of hydrogen sulfide is determined. According to the results of the analysis, the content of hydrogen sulfide in fuel oil after catalytic demercaptanization is 2.0 - 10% in May.
Пример 2. (сравнительный)Example 2. (comparative)
Демеркаптанизацию модельного мазута проводят как в Примере 1 , за исключением того, что в качестве каталитической системы используют катализатор на основе оксихлорида меди (II) и этаноламина без добавки триазина. Содержание сероводорода в мазуте после каталитической демеркаптанизации составляет 2,0« 10'3 % мае.The demercaptanization of model fuel oil is carried out as in Example 1, except that a catalyst based on copper (II) oxychloride and ethanolamine without the addition of triazine is used as a catalytic system. The content of hydrogen sulfide in fuel oil after catalytic demercaptanization is 2.0 “10 3 % in May.
Примеры 3 - 10.Examples 3 to 10
Демеркаптанизацию модельного мазута проводят как в Примере 1 , за исключением того, что изменяют параметры процесса, содержание и состав каталитической системы. Параметры процесса, содержание и состав каталитической системы, а также результаты демекаптанизации мазута представлены в Таблице 2.The demercaptanization of model fuel oil is carried out as in Example 1, except that the process parameters, the content and composition of the catalytic system are changed. The process parameters, the content and composition of the catalytic system, as well as the results of the demekaptization of fuel oil are presented in Table 2.
Из приведенных в табл. 2 экспериментальных данных видно, что при несоблюдении заявляемых соотношений катализатор/триазины, а также содержания окислителя (Примеры 5, 6, 7 и 8) степень удаления сероводорода снижается. В то же время природа используемого соединения переходного металла и азотсодержащего лиганда практически не сказывается на качестве демеркаптанизации.
Как видно из описания изобретения и примеров его осуществления заявляемый способ позволяет получить высокочистую нефти и нефтяные дистилляты за счет более полного окисления серосодержащих соединений и повышения стабильности каталитической системы при одновременном улучшении технико-экономических показателей процесса.From the above table. 2 experimental data shows that if the claimed ratios of the catalyst / triazines, as well as the content of the oxidizing agent (Examples 5, 6, 7 and 8), the degree of removal of hydrogen sulfide is reduced. At the same time, the nature of the used transition metal compound and nitrogen-containing ligand practically does not affect the quality of demercaptanization. As can be seen from the description of the invention and examples of its implementation, the inventive method allows to obtain high-purity oil and oil distillates due to more complete oxidation of sulfur-containing compounds and increase the stability of the catalytic system while improving the technical and economic indicators of the process.
Источники информации, принятые во внимание при составлении заявки.Sources of information taken into account when preparing the application.
RU 2145972 C1, М.кл. С 10 G 27/04, публ. 2000 г.RU 2145972 C1, M.C. With 10 G 27/04, publ. 2000 year
RU 2173330 C1 , М.кл. С 10 G 27/04, публ. 2001 г.RU 2173330 C1, M.cl. With 10 G 27/04, publ. 2001 year
WO 2006/094612, М.кл. С 10 G 27/00, публ. 2006 г.WO 2006/094612, M.C. With 10 G 27/00, publ. 2006 year
RU (94039238/04) C1 , М.кл. С 10 G 27/04, публ. 1997 г.RU (94039238/04) C1, M.C. With 10 G 27/04, publ. 1997 year
RU 2272065 C1, М.кл. С 10 G 27/04, публ. 2006 г.
RU 2272065 C1, M.C. With 10 G 27/04, publ. 2006 year
Claims
ФОРМУЛА ИЗОБРЕТЕНИЯ 8 SUMMARY OF THE INVENTION 8
СПОСОБ ОКИСЛИТЕЛЬНОЙ ДЕМЕРКАПТАНИЗАЦИИ НЕФТИ И НЕФТЯНЫХ ДИСТИЛЛЯТОВ.METHOD FOR OXIDATIVE DEMERCAPTANIZATION OF OIL AND OIL DISTILLATES.
МКИ С 10 G 27/04MKI S 10 G 27/04
Способ окислительной демеркаптанизации нефти и нефтяных дистиллятов включающий воздействие на мазут окислителя в присутствии катализатора, о т л и ч а ю щ и й с я тем, что в качестве катализатора используют смесь производного переходного металла связанного в комплекс с азотсодержащим лигандом и триазинами при соотношении комплекс производного переходного металла/триазины 1/3,0 - 1/4,0 и процесс ведут при рН реакционной среды 5,5 - 6,0 и температуре 20 - 1200C и в качестве окислителя используют азотно-воздушную смесь с содержанием кислорода не менее 3 % объемных.
The method of oxidative demercaptanization of oil and oil distillates, including the effect on the oxidizer fuel oil in the presence of a catalyst, which is based on the fact that a mixture of a transition metal derivative bound to a complex with a nitrogen-containing ligand and triazines is used as a catalyst at a complex ratio transition metal derivative / triazines 1 / 3.0 - 1 / 4.0 and the process is carried out at a pH of the reaction medium of 5.5 - 6.0 and a temperature of 20 - 120 0 C and a nitrogen-air mixture with an oxygen content not used as an oxidizing agent less 3% vol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EA200900595A EA012808B1 (en) | 2009-05-25 | 2009-05-25 | Process for oxidative oil demercaptanization and oil distillates |
| EA200900595 | 2009-05-25 |
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| WO2010136843A2 true WO2010136843A2 (en) | 2010-12-02 |
| WO2010136843A3 WO2010136843A3 (en) | 2011-02-24 |
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| PCT/IB2009/006516 WO2010136843A2 (en) | 2009-05-25 | 2009-08-05 | Method for removing mercaptans from crude oil and petroleum distillates by oxidation |
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| WO (1) | WO2010136843A2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU94039238A (en) | 1994-10-18 | 1996-12-10 | Всероссийский научно-исследовательский институт углеводородного сырья | Method for demercaptanization of oil distillates |
| RU2145972C1 (en) | 1998-05-25 | 2000-02-27 | Ахмадуллина Альфия Гариповна | Method of cleaning high-boiling hydrocarbon fractions from mercaptans and acid impurities |
| RU2173330C1 (en) | 2000-04-24 | 2001-09-10 | Ахмадуллина Альфия Гариповна | Method of decaptanization of hydrocarbon stock |
| RU2272065C2 (en) | 2004-04-29 | 2006-03-20 | ГУП РТ Всероссийский научно-исследовательский институт углеводородного сырья | Method of treating heavy petroleum to remove hydrogen sulfide |
| WO2006094612A1 (en) | 2005-03-03 | 2006-09-14 | Eni S.P.A. | Process for the removal by oxidation, of mercaptans contained in hydrocarbons |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1361305A (en) * | 1961-07-21 | 1964-05-22 | Cie De Raffinage Shell Berre | Process and catalyst for the preparation of hydrocarbon oils wholly or nearly wholly free of mercaptans |
| US4124494A (en) * | 1978-01-11 | 1978-11-07 | Uop Inc. | Treating a petroleum distillate with a supported metal phthalocyanine and an alkanolamine hydroxide |
| FR2573087B1 (en) * | 1984-11-09 | 1987-07-10 | Inst Francais Du Petrole | METHOD OF SOFTENING OIL CUTTINGS CARRIED OUT IN THE ABSENCE OF AN ALKALINE COMPOUND |
| US4753722A (en) * | 1986-06-17 | 1988-06-28 | Merichem Company | Treatment of mercaptan-containing streams utilizing nitrogen based promoters |
| CA2441971C (en) * | 2001-03-29 | 2010-10-19 | Framson Limited | Alkali-free demercaptanization catalyst for hydrocarbon compositions |
-
2009
- 2009-05-25 EA EA200900595A patent/EA012808B1/en not_active IP Right Cessation
- 2009-08-05 WO PCT/IB2009/006516 patent/WO2010136843A2/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU94039238A (en) | 1994-10-18 | 1996-12-10 | Всероссийский научно-исследовательский институт углеводородного сырья | Method for demercaptanization of oil distillates |
| RU2145972C1 (en) | 1998-05-25 | 2000-02-27 | Ахмадуллина Альфия Гариповна | Method of cleaning high-boiling hydrocarbon fractions from mercaptans and acid impurities |
| RU2173330C1 (en) | 2000-04-24 | 2001-09-10 | Ахмадуллина Альфия Гариповна | Method of decaptanization of hydrocarbon stock |
| RU2272065C2 (en) | 2004-04-29 | 2006-03-20 | ГУП РТ Всероссийский научно-исследовательский институт углеводородного сырья | Method of treating heavy petroleum to remove hydrogen sulfide |
| WO2006094612A1 (en) | 2005-03-03 | 2006-09-14 | Eni S.P.A. | Process for the removal by oxidation, of mercaptans contained in hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| EA200900595A2 (en) | 2009-08-28 |
| EA200900595A3 (en) | 2009-10-30 |
| EA012808B1 (en) | 2009-12-30 |
| WO2010136843A3 (en) | 2011-02-24 |
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