WO2021054855A1 - Catalyst for joint cracking of oil fractions - Google Patents

Catalyst for joint cracking of oil fractions Download PDF

Info

Publication number
WO2021054855A1
WO2021054855A1 PCT/RU2019/000970 RU2019000970W WO2021054855A1 WO 2021054855 A1 WO2021054855 A1 WO 2021054855A1 RU 2019000970 W RU2019000970 W RU 2019000970W WO 2021054855 A1 WO2021054855 A1 WO 2021054855A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
zeolite
fractions
oil
gasoline
Prior art date
Application number
PCT/RU2019/000970
Other languages
French (fr)
Russian (ru)
Inventor
Владимир Павлович ДОРОНИН
Олег Валерьевич ПОТАПЕНКО
Татьяна Павловна СОРОКИНА
Константин Игоревич ДМИТРИЕВ
Петр Владимирович ЛИПИН
Андрей Владимирович КЛЕЙМЕНОВ
Дмитрий Олегович КОНДРАШЕВ
Анна Вячеславовна АНДРЕЕВА
Дмитрий Валерьевич ХРАПОВ
Руслан Валерьевич ЕСИПЕНКО
Original Assignee
Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз")
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз") filed Critical Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз")
Publication of WO2021054855A1 publication Critical patent/WO2021054855A1/en

Links

Classifications

    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed

Definitions

  • the invention relates to the field of the oil refining industry, namely to catalysts for producing light olefins.
  • Light olefins - ethylene, propylene, butylenes - are currently used as raw materials both for petrochemicals and in the production of high-octane components of motor fuels.
  • One of the methods for producing olefins is catalytic cracking of hydrocarbon fractions on zeolite-containing catalysts.
  • the classic version of catalytic cracking involves the use of heavy oil fractions as feedstock: vacuum distillates, fuel oil, and various oil residues.
  • the petrochemical version of the process allows the use of light hydrocarbon fractions - kerosene-gas oil and gasoline - as raw materials.
  • Known catalyst for cracking a wide hydrocarbon fraction C4-C12 consisting of a phosphorus-modified zeolite ZSM-5 with a Si / Al ratio of 20-60, as well as silicon oxide, bentonite and kaolin clay (US patent 5171921).
  • the phosphorus content in the zeolite varies from 0.1 to 10% of the mass.
  • the disadvantages of this catalyst is the need for steam activation at a temperature of 500-700 ° C and a pressure of 1-5 atm. within 1-48 hours, low modulus of the original zeolite ZSM-5, and the use of an inactive matrix that reduces the overall activity of the catalyst.
  • Known catalyst for the cracking of hydrocarbons which is used in the production of light olefins in the cracking of fractions with a boiling point of 30-200 ° C, based on zeolite type ZSM-5, natural clay, inorganic oxide with the introduction of manganese oxide and phosphorus in the catalyst (patent RU 2494809) ...
  • the introduction of the phosphorus precursor is carried out on the catalyst composition or its constituents.
  • the disadvantage is also the low activity of the catalyst.
  • the closest to the proposed catalyst for the joint cracking of oil fractions is a vacuum gas oil cracking catalyst with a controlled yield of Cs and C4 olefins (patent RU 2554884, prototype).
  • the catalyst includes ultrastable zeolite Y in a cation-decationized form, zeolite HZSM-5 and a matrix, the components of which are used amorphous aluminosilicate, aluminum hydroxide and bentonite clay with the following content of components, wt%: zeolite Y 10-30; zeolite ZSM-5 10-30; bentonite clay 15-40; aluminum hydroxide 15-20; amorphous aluminosilicate 20-40.
  • the disadvantage of this catalyst is its limited use - only for the cracking of hydrotreated vacuum gas oil. It is an object of the present invention to provide a highly active petroleum co-cracking catalyst providing a high yield of light olefins.
  • the proposed catalyst for the joint cracking of petroleum fractions includes zeolite ZSM-5, ultrastable zeolite NRZEU and a matrix consisting of amorphous aluminosilicate, aluminum oxide and bentonite clay, and differs in that the zeolite ZSM-5 has a Si / Al ratio from 30 to 80, contains from 2.0 to 4.0 wt.% Phosphorus, with the following ratio of components in the catalyst, wt.%: Phosphorus-modified zeolite ZSM-5 8-20; ultrastable zeolite NRZEU 15-25; aluminum oxide 15-30; bentonite clay 15-30 and amorphous aluminosilicate 16-30.
  • non-hydrotreated vacuum gas oil As petroleum fractions, mixtures of non-hydrotreated vacuum gas oil with the following gasoline fractions are used: straight-run gasoline fraction 62-85 ° ⁇ , n.c.fraction. -70 ° ⁇ , gasoline - raffinate, mixtures of the indicated fractions.
  • the quality indicators of the used gasoline fractions are shown in Table 1.
  • the properties of non-hydrotreated vacuum gas oil are shown in Table 2.
  • table 2 The preparation of the catalyst composition is carried out by successive mixing of suspensions of its constituent components. The sequence of mixing the components during preparation is as follows:
  • the main requirement for the implementation of all stages of preparation of the catalyst composition is the homogeneous mixing of the suspensions of the components.
  • the resulting catalyst composition is molded.
  • the catalyst is dried first in air at room temperature, then at 100 ° C, calcined at 600 ° C.
  • the samples are treated in an environment of 100% steam at 788 ° C for 5 hours in accordance with ASTM D 4463.
  • Catalytic tests were performed on a laboratory flow-through unit with a fixed catalyst bed. Catalyst tests were performed for samples stabilized in water vapor (100% ⁇ , 788 ° ⁇ , 5 h).
  • the analysis of gaseous products was carried out on a GC-1000 chromatograph with a capillary column (S1O2, 30 m * 0.32 mm) and a flame ionization detector to determine the composition of hydrocarbon gases.
  • the coke content on the catalyst was determined from the weight loss upon calcining the catalyst sample to 650 ° C.
  • X 1 -Ezh, (1) where X is the conversion of raw materials, Ezh is the sum of the outputs of light and heavy gas oils.
  • the catalyst is prepared by mixing zeolite ZSM-5, zeolite HP33Y, bentonite clay, aluminum oxide from its hydroxide and amorphous aluminosilicate, followed by molding, drying and calcining in accordance with example 2 of the prototype.
  • the catalyst contains, May. %: zeolite HP33Y 20, zeolite HZSM-5 20, alumina 20, bentonite clay 20 and amorphous aluminosilicate 20.
  • the Si / Al ratio in zeolite ZSM-5 is 30.
  • Non-hydrotreated vacuum gas oil (NVGO) is cracked.
  • the reactor temperature is 540 ° C.
  • zeolite P-ZSM-5 with a Si / Al ratio of 30 is carried out by impregnating the zeolite HZSM-5 with a solution of (NH 4 ) 2 HP0 4 .
  • the impregnated zeolite is separated from the mother liquor, dried in air at room temperature for 24 hours, then at 100 ° C for 10 h, calcined at 600 ° C for 5 h.
  • the catalyst is prepared by mixing P-ZSM-5 zeolite with suspensions of HR33U zeolite, bentonite clay, reprecipitated aluminum hydroxide and amorphous aluminosilicate, followed by molding, drying the catalyst at 100 ° C for 12 h and calcining in air at 600 ° C for 5 h.
  • the catalyst contains 15% HR33U zeolite, PZSM-5 zeolite with 2% - 20% phosphorus, 20% alumina, 20% bentonite clay and 25% amorphous aluminosilicate.
  • a mixture of non-hydrotreated vacuum gas oil (85%) with a mixture of gasoline fractions is subjected to cracking - straight-run gasoline fraction 62-85 ° ⁇ , gasoline fraction n.c. -70 ° ⁇ , gasoline - raffinate - with a mass ratio of 1: 1: 2, respectively (15%).
  • the reactor temperature is 540 ° C.
  • the catalyst contains 20% HR33U zeolite, PZSM-5 zeolite with a phosphorus content of 2% - 20%, aluminum oxide 20%, bentonite clay 20% and amorphous aluminosilicate 20%.
  • a mixture of non-hydrotreated vacuum gas oil (85%) with a mixture of gasoline fractions (15%) is cracked.
  • the reactor temperature is 520 ° C.
  • Example 4 The catalyst contains 16 wt.% Zeolite HP33Y, 8% zeolite P / ZSM-5 with a Si / Al ratio of 40 and a phosphorus content of 4 wt.%, Bentonite clay 30%, aluminum oxide 30% and amorphous aluminosilicate 16 %. A mixture of non-hydrotreated vacuum gas oil (85%) with a mixture of gasoline fractions (15%) is cracked. The reactor temperature is 560 ° C.
  • Example 5 Similar to example 3, differs in that using a zeolite P / ZSM-5 with a Si / Al ratio of 80, and the phosphorus content in the zeolite 4%.
  • the catalyst contains bentonite clay 15 wt.%, Aluminum oxide 15 May. % and amorphous aluminosilicate 30 wt.%.
  • a mixture of non-hydrotreated vacuum gas oil (90%) with a mixture of gasoline fractions (10%) is cracked.
  • Example 6 The catalyst contains 25 wt.% Zeolite HP33Y, 15 wt.% Zeolite P / ZSM-5 with a Si / Al ratio of 40, and a phosphorus content of 4 wt.%, Bentonite clay 20 wt.%, Aluminum oxide 20 wt. ... % and amorphous aluminosilicate 20 wt.%.
  • a mixture of non-hydrotreated vacuum gas oil (85%) with a mixture of gasoline fractions (15%) is cracked.
  • Example 7 Similar to example 3, but a mixture of non-hydrotreated vacuum gas oil (85%) and raffinate gasoline (15%) is subjected to cracking. Reactor temperature 530 ° C.
  • Example 8 Similar to example 3, but a mixture of non-hydrotreated vacuum gas oil (85%) and gasoline fraction 62-85 ° C (15%) is subjected to cracking. Reactor temperature 530 ° C.
  • Example 9 Analogous to example 3, but a mixture of non-hydrotreated vacuum gas oil (85%) and n.c. gasoline fraction is cracked. - 70 ° C (15%). Reactor temperature 530 ° C.
  • the use of the proposed new effective catalyst for the joint cracking of petroleum fractions provides high yields of light olefinic hydrocarbons (ethylene, propylene and butylenes).
  • an additional result of the invention is the expansion of the feedstock base by attracting low-grade gasoline fractions for the production of light olefins and high-quality commercial gasolines.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to the field of oil-refining, and more particularly to catalysts for obtaining light olefins. The proposed catalyst for joint cracking of oil fractions includes zeolite ZSM-5, ultra-stable zeolite HREY and a matrix comprising amorphous aluminosilicate, aluminum oxide and bentonite clay, and is characterized in that the zeolite ZSM-5 has a Si/Al ratio of 30 to 80 and contains 2.0 to 4.0 wt% of phosphorus, the catalyst containing the following relative amounts of components, in wt%: 8-20 phosphorus-modified zeolite ZSM-5; 15-25 ultra-stable zeolite HREY; 15-30 aluminum oxide; 15-30 bentonite clay; and 16-30 amorphous aluminosilicate. Mixtures of non-hydrotreated vacuum gas oil with the following gasoline fractions are used as the oil fractions: straight-run gasoline fraction 62-85C, a fraction with a boiling point of 70C, gasoline refined oil, a mixture of the specified fractions. The technical result is that of obtaining a highly active catalyst for joint cracking of oil fractions which provides high yields of light olefin hydrocarbons.

Description

КАТАЛИЗАТОР СОВМЕСТНОГО КРЕКИНГА НЕФТЯНЫХ OIL JOINT CRACKING CATALYST
ФРАКЦИЙ FRACTIONS
Изобретение относится к области нефтеперерабатывающей промышленности, а именно к катализаторам для получения легких олефинов. The invention relates to the field of the oil refining industry, namely to catalysts for producing light olefins.
Легкие олефины - этилен, пропилен, бутилены — в настоящее время находят применение в качестве сырья, как для нефтехимии, так и при производстве высокооктановых компонентов моторных топлив. Одним из способов получения олефинов является каталитический крекинг углеводородных фракций на цеолитсодержащих катализаторах. Классический вариант каталитического крекинга подразумевает использование в качестве сырья тяжелых нефтяных фракций: вакуумных дистиллятов, мазута, различных нефтяных остатков. Нефтехимический вариант процесса допускает возможность использования в качестве сырья легких углеводородных фракций - керосино-газойлевых и бензиновых. В ряде случаев возникает необходимость совместной переработки легких и тяжелых нефтяных фракций в процессе каталитического крекинга, где в качестве легких могут выступать низкосортные бензиновые фракции, не находящие рационального применения в структуре современных нефтеперерабатывающих предприятий. Для обеспечения эффективного совместного крекинга требуется разработка специализированных катализаторов. Light olefins - ethylene, propylene, butylenes - are currently used as raw materials both for petrochemicals and in the production of high-octane components of motor fuels. One of the methods for producing olefins is catalytic cracking of hydrocarbon fractions on zeolite-containing catalysts. The classic version of catalytic cracking involves the use of heavy oil fractions as feedstock: vacuum distillates, fuel oil, and various oil residues. The petrochemical version of the process allows the use of light hydrocarbon fractions - kerosene-gas oil and gasoline - as raw materials. In a number of cases, it becomes necessary to jointly process light and heavy oil fractions in the process of catalytic cracking, where low-grade gasoline fractions, which are not rationally used in the structure of modern oil refineries, can act as light ones. Effective co-cracking requires the development of specialized catalysts.
Известен катализатор крекинга широкой углеводородной фракции С4- С12, состоящий из модифицированного фосфором цеолита ZSM-5 с отношением Si/Al, равным 20-60, а также оксида кремния, бентонитовой и каолиновой глины (патент US 5171921). Содержание фосфора в цеолите варьируется от 0,1 до 10 % масс. Недостатками данного катализатора является необходимость паровой активации при температуре 500-700 °С и давлении 1- 5 атм. в течение 1-48 ч, низкий модуль исходного цеолита ZSM-5, а также использование неактивной матрицы, уменьшающей общую активность катализатора. Known catalyst for cracking a wide hydrocarbon fraction C4-C12, consisting of a phosphorus-modified zeolite ZSM-5 with a Si / Al ratio of 20-60, as well as silicon oxide, bentonite and kaolin clay (US patent 5171921). The phosphorus content in the zeolite varies from 0.1 to 10% of the mass. The disadvantages of this catalyst is the need for steam activation at a temperature of 500-700 ° C and a pressure of 1-5 atm. within 1-48 hours, low modulus of the original zeolite ZSM-5, and the use of an inactive matrix that reduces the overall activity of the catalyst.
Известен катализатор крекинга углеводородов, содержащий 20-50 мае. % цеолита ZSM-5, 10-45 мае. % глины, 10-45 мае. % неорганического оксида, 1-10 мае. % одного или нескольких металлов и 5-15 мас.% фосфора для увеличения выхода сжиженных газов, в котором модификацию фосфором проводят для цеолита ZSM-5 (патент RU 2397811). Недостатком является низкая активность катализатора. Known catalyst for the cracking of hydrocarbons containing 20-50 May. % zeolite ZSM-5, May 10-45. % clay, May 10-45. % inorganic oxide, May 1-10. % of one or more metals and 5-15 wt.% phosphorus to increase the yield of liquefied gases, in which the modification with phosphorus is carried out for zeolite ZSM-5 (patent RU 2397811). The disadvantage is the low activity of the catalyst.
Известен катализатор крекинга углеводородов, который применяют при получении легких олефинов при крекинге фракции с пределами температур кипения 30-200°С, на основе цеолита типа ZSM-5, природной глины, неорганического оксида с внесением оксида марганца и фосфора в катализатор (патент RU 2494809). Внесение предшественника фосфора осуществляют на композицию катализатора или его составляющие. Недостатком также является низкая активность катализатора. Known catalyst for the cracking of hydrocarbons, which is used in the production of light olefins in the cracking of fractions with a boiling point of 30-200 ° C, based on zeolite type ZSM-5, natural clay, inorganic oxide with the introduction of manganese oxide and phosphorus in the catalyst (patent RU 2494809) ... The introduction of the phosphorus precursor is carried out on the catalyst composition or its constituents. The disadvantage is also the low activity of the catalyst.
Известен катализатор крекинга нефтяных фракций с использованием кислотного цеолита с малыми и средними порами (патент US 6080303, аналог заявка RU 2000125817). Способ его получения включает стадии обработки кислотного цеолита с малыми или средними порами 0,5-10 мас.% соединения фосфора с получением обработанного фосфором цеолита и совмещения этого обработанного фосфором цеолита с 1-50 мас.% AIPO4 в пересчете на массу цеолита. При этом крекингу на указанном катализаторе подвергаются бензиновые и бензино-лигроиновые фракции. Недостатком данного катализатора является низкий выход легких олефинов. Known catalyst for cracking petroleum fractions using an acidic zeolite with small and medium pores (US patent 6080303, analogous application RU 2000125817). The method for its preparation includes the stages of processing an acidic zeolite with small or medium pores of 0.5-10 wt.% Of a phosphorus compound to obtain a phosphorus-treated zeolite and combining this phosphorus-treated zeolite with 1-50 wt.% AIPO4 based on the weight of the zeolite. In this case, gasoline and gasoline-naphtha fractions are subjected to cracking on the specified catalyst. The disadvantage of this catalyst is the low yield of light olefins.
Наиболее близким к предлагаемому катализатору совместного крекинга нефтяных фракций является катализатор крекинга вакуумного газойля с регулируемым выходом олефинов Сз и С4 (патент RU 2554884, прототип). Катализатор включает ультрастабильный цеолит Y в катион- декатионированной форме, цеолит HZSM-5 и матрицу, в качестве компонентов которой используют аморфный алюмосиликат, гидроксид алюминия и бентонитовую глину при следующем содержании компонентов, мас.%: цеолит Y 10-30; цеолит ZSM-5 10-30; бентонитовая глина 15-40; гидроксид алюминия 15-20; аморфный алюмосиликат 20-40. Недостатком данного катализатора является его ограниченное использование - только для крекинга гидроочищенного вакуумного газойля. Целью настоящего изобретения является получение высокоактивного катализатора совместного крекинга нефтяных фракций, обеспечивающего высокий выход легких олефинов. The closest to the proposed catalyst for the joint cracking of oil fractions is a vacuum gas oil cracking catalyst with a controlled yield of Cs and C4 olefins (patent RU 2554884, prototype). The catalyst includes ultrastable zeolite Y in a cation-decationized form, zeolite HZSM-5 and a matrix, the components of which are used amorphous aluminosilicate, aluminum hydroxide and bentonite clay with the following content of components, wt%: zeolite Y 10-30; zeolite ZSM-5 10-30; bentonite clay 15-40; aluminum hydroxide 15-20; amorphous aluminosilicate 20-40. The disadvantage of this catalyst is its limited use - only for the cracking of hydrotreated vacuum gas oil. It is an object of the present invention to provide a highly active petroleum co-cracking catalyst providing a high yield of light olefins.
Предлагаемый катализатор совместного крекинга нефтяных фракций включает цеолит ZSM-5, ультрастабильный цеолит НРЗЭУ и матрицу, состоящую из аморфного алюмосиликата, оксида алюминия и бентонитовой глины, и отличается тем, что цеолит ZSM-5 имеет отношение Si/Al от 30 до 80, содержит от 2,0 до 4,0 мас.% фосфора, при следующем соотношении компонентов в катализаторе, мас.%: модифицированный фосфором цеолит ZSM-5 8-20; ультрастабильный цеолит НРЗЭУ 15-25; оксид алюминия 15-30; бентонитовая глина 15-30 и аморфный алюмосиликат 16-30. The proposed catalyst for the joint cracking of petroleum fractions includes zeolite ZSM-5, ultrastable zeolite NRZEU and a matrix consisting of amorphous aluminosilicate, aluminum oxide and bentonite clay, and differs in that the zeolite ZSM-5 has a Si / Al ratio from 30 to 80, contains from 2.0 to 4.0 wt.% Phosphorus, with the following ratio of components in the catalyst, wt.%: Phosphorus-modified zeolite ZSM-5 8-20; ultrastable zeolite NRZEU 15-25; aluminum oxide 15-30; bentonite clay 15-30 and amorphous aluminosilicate 16-30.
В качестве нефтяных фракций используют смеси негидроочищенного вакуумного газойля со следующими бензиновыми фракциями: прямогонная бензиновая фракция 62-85°С, фракция н.к. -70 °С, бензин - рафинат, смеси указанных фракций. Показатели качества используемых бензиновых фракций приведены в таблице 1. Свойства негидроочищенного вакуумного газойля приведены в таблице 2. As petroleum fractions, mixtures of non-hydrotreated vacuum gas oil with the following gasoline fractions are used: straight-run gasoline fraction 62-85 ° С, n.c.fraction. -70 ° С, gasoline - raffinate, mixtures of the indicated fractions. The quality indicators of the used gasoline fractions are shown in Table 1. The properties of non-hydrotreated vacuum gas oil are shown in Table 2.
Таблица 1
Figure imgf000005_0001
Figure imgf000006_0001
Table 1
Figure imgf000005_0001
Figure imgf000006_0001
Таблица 2
Figure imgf000006_0002
Приготовление катализаторной композиции выполняют путем последовательного смешения суспензий составляющих ее компонентов. Последовательность смешения компонентов при приготовлении следующая: table 2
Figure imgf000006_0002
The preparation of the catalyst composition is carried out by successive mixing of suspensions of its constituent components. The sequence of mixing the components during preparation is as follows:
1) приготовление алюминийсодержащего компонента в результате смешения суспензий бентонитовой глины и переосажденного гидроксида алюминия в необходимом соотношении; 1) preparation of an aluminum-containing component as a result of mixing suspensions of bentonite clay and reprecipitated aluminum hydroxide in the required ratio;
2) ввод в суспензию алюминийсодержащего компонента суспензии цеолита ZSM-5, содержащего фосфор, и ультрастабильного цеолита HP33Y; 2) introducing into the suspension the aluminum-containing component of the suspension of the ZSM-5 zeolite containing phosphorus and the ultrastable zeolite HP33Y;
3) добавление к полученной суспензии рассчитанного количества суспензии аморфного алюмосиликата. 3) adding to the resulting suspension the calculated amount of the suspension of amorphous aluminosilicate.
Основным требованием к осуществлению всех стадий приготовления катализаторной композиции является гомогенное смешение суспензий компонентов. Полученную композицию катализаторов формуют. Далее катализатор сушат сначала на воздухе при комнатной температуре, затем при 100 °С, прокаливают при 600 °С. Для оценки стабильной активности катализаторов образцы обрабатывают в среде 100 % водяного пара при 788 °С в течение 5 ч в соответствии с ASTM D 4463. The main requirement for the implementation of all stages of preparation of the catalyst composition is the homogeneous mixing of the suspensions of the components. The resulting catalyst composition is molded. Next, the catalyst is dried first in air at room temperature, then at 100 ° C, calcined at 600 ° C. To assess the stable activity of the catalysts, the samples are treated in an environment of 100% steam at 788 ° C for 5 hours in accordance with ASTM D 4463.
Каталитические испытания выполнены на лабораторной проточной установке с неподвижным слоем катализатора. Испытания катализаторов выполнены для стабилизированных в среде водяного пара (100 % НгО, 788 °С, 5 ч) образцов. Catalytic tests were performed on a laboratory flow-through unit with a fixed catalyst bed. Catalyst tests were performed for samples stabilized in water vapor (100% НгО, 788 ° С, 5 h).
Анализ газообразных продуктов осуществляли на хроматографе «ГХ- 1000» с капиллярной колонкой (S1O2, 30 м * 0.32 мм) и пламенно- ионизационным детектором для определения состава углеводородных газов. Содержание кокса на катализаторе определяли по убыли массы при прокаливании образца катализатора до 650 °С. The analysis of gaseous products was carried out on a GC-1000 chromatograph with a capillary column (S1O2, 30 m * 0.32 mm) and a flame ionization detector to determine the composition of hydrocarbon gases. The coke content on the catalyst was determined from the weight loss upon calcining the catalyst sample to 650 ° C.
Конверсию сырья рассчитывали по формуле: The conversion of raw materials was calculated by the formula:
Х= 1 -Еж, (1) где X — конверсия сырья, Еж - сумма выходов легкого и тяжелого газойлей. X = 1 -Ezh, (1) where X is the conversion of raw materials, Ezh is the sum of the outputs of light and heavy gas oils.
Состав катализаторов и результаты испытаний приведены в таблице 3. Сущность изобретения иллюстрируется следующими примерами.The composition of the catalysts and the test results are shown in Table 3. The essence of the invention is illustrated by the following examples.
Пример 1. (сравнительный по прототипу). Example 1. (comparative for the prototype).
Катализатор готовят путем смешения цеолита ZSM-5, цеолита HP33Y, бентонитовой глины, оксида алюминия из его гидроксида и аморфного алюмосиликата с последующей формовкой, сушкой и прокалкой в соответствии с примером 2 по прототипу. Катализатор содержит, мае. %: цеолит HP33Y 20, цеолит HZSM-5 20, оксид алюминия 20, бентонитовая глина 20 и аморфный алюмосиликат 20. Отношение Si/Al в цеолите ZSM-5 равно 30. The catalyst is prepared by mixing zeolite ZSM-5, zeolite HP33Y, bentonite clay, aluminum oxide from its hydroxide and amorphous aluminosilicate, followed by molding, drying and calcining in accordance with example 2 of the prototype. The catalyst contains, May. %: zeolite HP33Y 20, zeolite HZSM-5 20, alumina 20, bentonite clay 20 and amorphous aluminosilicate 20. The Si / Al ratio in zeolite ZSM-5 is 30.
Крекингу подвергают негидроочищенный вакуумный газойль (НВГО). Температура реактора равна 540 °С. Non-hydrotreated vacuum gas oil (NVGO) is cracked. The reactor temperature is 540 ° C.
Пример 2. Example 2.
Получение цеолита P-ZSM-5 с отношением Si/Al, равным 30, осуществляют путем пропитки цеолита HZSM-5 раствором (NH4)2HP04. Пропитанный цеолит отделяют от маточного раствора, сушат сутки на воздухе при комнатной температуре, затем при 100°С в течение 10 ч, прокаливают при 600 °С в течение 5 ч. Катализатор готовят путем смешения цеолита P-ZSM-5 с суспензиями цеолита HR33U, бентонитовой глины, переосажденного гидроксида алюминия и аморфного алюмосиликата, с последующей формовкой, сушкой катализатора при 100 °С в течение 12 ч и прокалкой в атмосфере воздуха при температуре 600 °С в течение 5 ч. Obtaining zeolite P-ZSM-5 with a Si / Al ratio of 30 is carried out by impregnating the zeolite HZSM-5 with a solution of (NH 4 ) 2 HP0 4 . The impregnated zeolite is separated from the mother liquor, dried in air at room temperature for 24 hours, then at 100 ° C for 10 h, calcined at 600 ° C for 5 h. The catalyst is prepared by mixing P-ZSM-5 zeolite with suspensions of HR33U zeolite, bentonite clay, reprecipitated aluminum hydroxide and amorphous aluminosilicate, followed by molding, drying the catalyst at 100 ° C for 12 h and calcining in air at 600 ° C for 5 h.
Катализатор содержит 15 % цеолита HR33U, цеолита PZSM-5 с содержанием фосфора 2 % - 20 %, оксида алюминия 20 %, бентонитовой глины 20 % и аморфного алюмосиликата 25 %. Крекингу подвергают смесь негидроочищенного вакуумного газойля (85 %) со смесью бензиновых фракций - прямогонная бензиновая фракция 62-85°С, бензиновая фракция н.к. -70 °С, бензин - рафинат - с массовым соотношением 1 : 1 : 2, соответственно, (15 %). Температура реактора равна 540 °С. The catalyst contains 15% HR33U zeolite, PZSM-5 zeolite with 2% - 20% phosphorus, 20% alumina, 20% bentonite clay and 25% amorphous aluminosilicate. A mixture of non-hydrotreated vacuum gas oil (85%) with a mixture of gasoline fractions is subjected to cracking - straight-run gasoline fraction 62-85 ° С, gasoline fraction n.c. -70 ° С, gasoline - raffinate - with a mass ratio of 1: 1: 2, respectively (15%). The reactor temperature is 540 ° C.
Пример 3. Example 3.
Аналогичен примеру 2, отличается тем, что катализатор содержит 20 % цеолита HR33U, цеолита PZSM-5 с содержанием фосфора 2 % - 20 %, оксида алюминия 20 %, бентонитовой глины 20 % и аморфного алюмосиликата 20 %. Крекингу подвергают смесь негидроочищенного вакуумного газойля (85 %) со смесью бензиновых фракций (15 %). Температура реактора равна 520 °С. Similar to example 2, it differs in that the catalyst contains 20% HR33U zeolite, PZSM-5 zeolite with a phosphorus content of 2% - 20%, aluminum oxide 20%, bentonite clay 20% and amorphous aluminosilicate 20%. A mixture of non-hydrotreated vacuum gas oil (85%) with a mixture of gasoline fractions (15%) is cracked. The reactor temperature is 520 ° C.
Пример 4. Катализатор содержит 16 мас.% цеолита HP33Y, 8 % цеолита P/ZSM-5 с отношением Si/Al, равным 40, и содержанием фосфора 4 мас.%, бентонитовой глины 30 %, оксида алюминия 30 % и аморфного алюмосиликата 16 %. Крекингу подвергают смесь негидроочищенного вакуумного газойля (85 %) со смесью бензиновых фракций (15%). Температура реактора равна 560 °С. Example 4. The catalyst contains 16 wt.% Zeolite HP33Y, 8% zeolite P / ZSM-5 with a Si / Al ratio of 40 and a phosphorus content of 4 wt.%, Bentonite clay 30%, aluminum oxide 30% and amorphous aluminosilicate 16 %. A mixture of non-hydrotreated vacuum gas oil (85%) with a mixture of gasoline fractions (15%) is cracked. The reactor temperature is 560 ° C.
Пример 5. Аналогичен примеру 3, отличается тем, что используют цеолит P/ZSM-5 с отношением Si/Al, равным 80, и содержание фосфора в цеолите 4 %. Катализатор содержит бентонитовой глины 15 мас.%, оксида алюминия 15 мае. % и аморфного алюмосиликата 30 мас.%. Крекингу подвергают смесь негидроочищенного вакуумного газойля (90 %) со смесью бензиновых фракций (10 %). Температура реактора 560 °С. Example 5. Similar to example 3, differs in that using a zeolite P / ZSM-5 with a Si / Al ratio of 80, and the phosphorus content in the zeolite 4%. The catalyst contains bentonite clay 15 wt.%, Aluminum oxide 15 May. % and amorphous aluminosilicate 30 wt.%. A mixture of non-hydrotreated vacuum gas oil (90%) with a mixture of gasoline fractions (10%) is cracked. Reactor temperature 560 ° C.
Пример 6. Катализатор содержит 25 мас.% цеолита HP33Y, 15 мас.% цеолита P/ZSM-5 с отношением Si/Al, равным 40, и содержанием фосфора 4 мас.%, бентонитовой глины 20 мас.%, оксида алюминия 20 мае. % и аморфного алюмосиликата 20 мас.%. Крекингу подвергают смесь негидроочищенного вакуумного газойля (85 %) со смесью бензиновых фракций (15 %). Температура реактора 530 °С. Example 6. The catalyst contains 25 wt.% Zeolite HP33Y, 15 wt.% Zeolite P / ZSM-5 with a Si / Al ratio of 40, and a phosphorus content of 4 wt.%, Bentonite clay 20 wt.%, Aluminum oxide 20 wt. ... % and amorphous aluminosilicate 20 wt.%. A mixture of non-hydrotreated vacuum gas oil (85%) with a mixture of gasoline fractions (15%) is cracked. Reactor temperature 530 ° C.
Пример 7. Аналогичен примеру 3, но крекингу подвергают смесь негидроочищенного вакуумного газойля (85 %) и бензина-рафината (15 %). Температура реактора 530 °С. Example 7. Similar to example 3, but a mixture of non-hydrotreated vacuum gas oil (85%) and raffinate gasoline (15%) is subjected to cracking. Reactor temperature 530 ° C.
Пример 8. Аналогичен примеру 3, но крекингу подвергают смесь негидроочищенного вакуумного газойля (85 %) и бензиновой фракции 62-85 °С (15 %). Температура реактора 530 °С. Example 8. Similar to example 3, but a mixture of non-hydrotreated vacuum gas oil (85%) and gasoline fraction 62-85 ° C (15%) is subjected to cracking. Reactor temperature 530 ° C.
Пример 9. Аналогичен примеру 3, но крекингу подвергают смесь негидроочищенного вакуумного газойля (85 %) и бензиновой фракции н.к. - 70 °С (15 %). Температура реактора 530 °С. Таким образом, как следует из примеров и таблицы 3, использование предлагаемого нового эффективного катализатора совместного крекинга нефтяных фракций обеспечивает высокие выходы легких олефиновых углеводородов (этилен, пропилен и бутил ены). Кроме того, дополнительным результатом изобретения является расширение сырьевой базы за счет привлечения низкосортных бензиновых фракций для получения легких олефинов и качественных товарных бензинов. Example 9. Analogous to example 3, but a mixture of non-hydrotreated vacuum gas oil (85%) and n.c. gasoline fraction is cracked. - 70 ° C (15%). Reactor temperature 530 ° C. Thus, as follows from the examples and table 3, the use of the proposed new effective catalyst for the joint cracking of petroleum fractions provides high yields of light olefinic hydrocarbons (ethylene, propylene and butylenes). In addition, an additional result of the invention is the expansion of the feedstock base by attracting low-grade gasoline fractions for the production of light olefins and high-quality commercial gasolines.
Таблица 3
Figure imgf000011_0001
Table 3
Figure imgf000011_0001
ЗАМЕНЯЮЩИЙ ЛИСТ (ПРАВИЛО 26)
Figure imgf000012_0001
SUBSTITUTE SHEET (RULE 26)
Figure imgf000012_0001
ЗАМЕНЯЮЩИЙ ЛИСТ (ПРАВИЛО 26) SUBSTITUTE SHEET (RULE 26)

Claims

Формула изобретения «Катализатор совместного крекинга нефтяных фракций» Formula of invention "Catalyst for joint cracking of petroleum fractions"
1. Катализатор совместного крекинга нефтяных фракций, включающий цеолит ZSM-5, ультрастабильный цеолит HP33Y и матрицу, состоящую из аморфного алюмосиликата, оксида алюминия и бентонитовой глины, отличающийся тем, что цеолит ZSM-5 имеет отношение Si/Al от 30 до 80, содержит от 2,0 до 4,0 мас.% фосфора, при следующем соотношении компонентов в катализаторе, мас.%: модифицированный фосфором цеолит ZSM-5 8-20; ультрастабильный цеолит НРЗЭУ 15-25; оксид алюминия 15-30; бентонитовая глина 15-30 и аморфный алюмосиликат 16-30. 1. Catalyst for joint cracking of petroleum fractions, including zeolite ZSM-5, ultrastable zeolite HP33Y and a matrix consisting of amorphous aluminosilicate, aluminum oxide and bentonite clay, characterized in that the zeolite ZSM-5 has a Si / Al ratio of 30 to 80, contains from 2.0 to 4.0 wt.% phosphorus, with the following ratio of components in the catalyst, wt.%: modified with phosphorus zeolite ZSM-5 8-20; ultrastable zeolite NRZEU 15-25; aluminum oxide 15-30; bentonite clay 15-30 and amorphous aluminosilicate 16-30.
2. Катализатор совместного крекинга нефтяных фракций по п.1, отличающийся тем, что в качестве нефтяных фракций используют смеси негидроочищенного вакуумного газойля со следующими бензиновыми фракциями: прямогонная бензиновая фракция 62-85°С, фракция н.к. -70 °С, бензин - рафинат, смеси указанных фракций. 2. A catalyst for joint cracking of petroleum fractions according to claim 1, characterized in that mixtures of non-hydrotreated vacuum gas oil with the following gasoline fractions are used as oil fractions: straight-run gasoline fraction 62-85 ° C, n.c.fraction. -70 ° С, gasoline - raffinate, mixtures of the indicated fractions.
ЗАМЕНЯЮЩИЙ ЛИСТ (ПРАВИЛО 26) SUBSTITUTE SHEET (RULE 26)
PCT/RU2019/000970 2019-09-16 2019-12-18 Catalyst for joint cracking of oil fractions WO2021054855A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2019129200A RU2709522C1 (en) 2019-09-16 2019-09-16 Catalyst for joint cracking of petroleum fractions
RU2019129200 2019-09-16

Publications (1)

Publication Number Publication Date
WO2021054855A1 true WO2021054855A1 (en) 2021-03-25

Family

ID=69006602

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2019/000970 WO2021054855A1 (en) 2019-09-16 2019-12-18 Catalyst for joint cracking of oil fractions

Country Status (2)

Country Link
RU (1) RU2709522C1 (en)
WO (1) WO2021054855A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2760552C1 (en) * 2021-03-01 2021-11-29 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть-ОНПЗ") Metal-resistant cracking catalyst and method for its preparation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4472518A (en) * 1981-11-04 1984-09-18 Mobil Oil Corporation Shape selective reactions with zeolite catalysts modified with iron and/or cobalt
RU2469070C1 (en) * 2011-10-13 2012-12-10 Учреждение Российской академии наук Институт проблем переработки углеводородов Сибирского отделения РАН (ИППУ СО РАН) Processing method of gasolines of thermal processes, and catalyst for its implementation

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1037327C (en) * 1990-06-20 1998-02-11 中国石油化工总公司石油化工科学研究院 Splitting catalyst containing high-silicon zeolite
US6835863B2 (en) * 1999-07-12 2004-12-28 Exxonmobil Oil Corporation Catalytic production of light olefins from naphtha feed
RU2362796C1 (en) * 2008-05-29 2009-07-27 ООО "Компания Катахим" Method of obtaining motor fuels
RU2548362C2 (en) * 2009-06-25 2015-04-20 Чайна Петролеум & Кемикал Корпорейшн Catalyst for catalytic cracking and method of increasing catalyst selectivity (versions)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4472518A (en) * 1981-11-04 1984-09-18 Mobil Oil Corporation Shape selective reactions with zeolite catalysts modified with iron and/or cobalt
RU2469070C1 (en) * 2011-10-13 2012-12-10 Учреждение Российской академии наук Институт проблем переработки углеводородов Сибирского отделения РАН (ИППУ СО РАН) Processing method of gasolines of thermal processes, and catalyst for its implementation

Also Published As

Publication number Publication date
RU2709522C1 (en) 2019-12-18

Similar Documents

Publication Publication Date Title
US10105690B2 (en) Bound catalyst for selective conversion of oxygenates to aromatics
US10494574B2 (en) Systems and methods for cracking hydrocarbon streams such as crude oils utilizing catalysts which include zeolite mixtures
CN107971010B (en) Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon
US9919985B2 (en) Additives for maximizing light olefins in fluid catalytic cracking and process units
CN101747129B (en) Method for producing light olefins through catalytic conversion
US20130001129A1 (en) Catalytic conversion method for increasing cetane number barrel of diesel
CN110479361A (en) A kind of drop slurry oil and the auxiliary agent of low-carbon olefines high-output and the preparation method and application thereof
CN109675616B (en) Catalytic conversion catalyst for producing more butene, preparation method of catalytic conversion catalyst and catalytic conversion method for producing more butene
WO2021054855A1 (en) Catalyst for joint cracking of oil fractions
US11401474B2 (en) Systems and methods for producing fuel intermediates
US10526546B2 (en) Systems and methods for cracking hydrocarbon streams utilizing cracking catalysts
RU2710856C1 (en) Method for joint oil fraction cracking
AU2016396601B2 (en) Method and catalyst for producing high octane components
RU2709521C1 (en) Oil fractions cracking catalyst
RU2710855C1 (en) Method of oil fractions cracking
US20230313050A1 (en) Catalytic cracking additive, preparation method therefor, and application thereof
Potapenko et al. Catalytic cracking of cyclohexane and 1-hexene mixtures on mono-, bi-, and tri-zeolite catalysts
WO2021043018A1 (en) Method for improving quality of oil product and increasing yield of low carbon olefin using catalytic cracking of bio-oil
EA043214B1 (en) CATALYST FOR CRACKING OF OIL FRACTIONS
Hiramatsu et al. Effect of acid properties of catalysts on fluid catalytic cracking of residual oil
RU2688662C1 (en) Method of catalytic cracking of butane-butylene fraction and catalyst for its implementation
Triantafyllidis et al. 5 State-of-the-art in biomass fast pyrolysis using acidic catalysts: direct comparison between microporous zeolites, mesoporous aluminosilicates and hierarchical zeolites
EP0698074A1 (en) Process for hydrocracking hydrocarbons
Esgair Investigating the Influence of the Cerium loading in prepared Y zeolite from Iraqi kaolin on its Catalytic Performance
CN116410048A (en) Preparation method of low-carbon olefin

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19945761

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19945761

Country of ref document: EP

Kind code of ref document: A1