WO2018052341A1 - Catalyseur d'isomérisation de n-alcanes dans un processus de reformage de fractions d'essence hydro-purifiées (variantes) - Google Patents

Catalyseur d'isomérisation de n-alcanes dans un processus de reformage de fractions d'essence hydro-purifiées (variantes) Download PDF

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WO2018052341A1
WO2018052341A1 PCT/RU2017/000666 RU2017000666W WO2018052341A1 WO 2018052341 A1 WO2018052341 A1 WO 2018052341A1 RU 2017000666 W RU2017000666 W RU 2017000666W WO 2018052341 A1 WO2018052341 A1 WO 2018052341A1
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catalyst
zeolite
mass
silicoaluminophosphate
sapo
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PCT/RU2017/000666
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English (en)
Russian (ru)
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Вадим Владимирович ФАДЕЕВ
Анна Всеволодовна АБРАМОВА
Денис Николаевич ГЕРАСИМОВ
Левон Львович ХЕМЧЯН
Анна Николаевна ЛОГИНОВА
Денис Владимирович ЛЯМИН
Екатерина Григорьевна ПЕТРОВА
Надежда Юрьевна УВАРОВА
Роман Алексеевич СМОЛИН
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Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть")
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Publication of WO2018052341A1 publication Critical patent/WO2018052341A1/fr

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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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
    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation

Definitions

  • the invention relates to the field of catalysis and oil refining, in particular, to a catalyst based on silicoaluminophosphate zeolites of the ATO and / or AEL structure, which efficiently provides isomerization of normal alkanes in the process of reforming hydrotreated gasoline fractions, and a method for its preparation.
  • a catalyst based on silicoaluminophosphate zeolites of the ATO and / or AEL structure which efficiently provides isomerization of normal alkanes in the process of reforming hydrotreated gasoline fractions, and a method for its preparation.
  • the target reactions include: dehydrogenation of naphthenic hydrocarbons ⁇ to arenas, " isomerization of five-membered cycloalkanes to cyclohexane derivatives, isomerization of n-alkanes to iso-alkanes, dehydrocyclization of alkanes to naphthenic and aromatic hydrocarbons, dehydrogenation of alkanes to hydroxy alkanes; as well as condensation reactions leading to coke deposition on the catalyst.
  • - zeolite catalysts mainly medium temperature isomerization (250-300 ° C),
  • fluorinated aluminoplatinum catalysts are characterized by an undesirably high operating temperature range, which inevitably leads to an increase in energy costs.
  • Chlorinated alumina catalysts have a low operating temperature range, providing a high yield of isomerizate, however, during isomerization, the chlorine content in these catalysts decreases, which quickly leads to a significant decrease in activity.
  • the introduction of chlorine-containing compounds (usually CC) into the processed feed is provided to maintain a high activity of the catalyst, which, in turn, necessitates the further capture of chlorine derivatives (alkaline washing).
  • CC chlorine-containing compounds
  • Zeolite catalysts have a relatively low operating temperature range, while differing in their exceptional resistance to poisonous impurities in raw materials and the ability to fully regenerate, thereby presenting a favorable compromise between alumina-platinum fluorinated catalysts and chlorinated alumina catalysts.
  • zeolites The uniqueness of zeolites lies in a comprehensive set of properties: acidity, porosity, structure of the crystal lattice, sorption ability, the possibility of ion exchange, etc.
  • zeolites serve as an additional effective tool in the production of catalysts used in the oil refining industry.
  • Literary examples of zeolite isomerization catalysts are presented by a number of systems, overwhelmingly, based on various aluminosilicates. Separate representative examples are provided below.
  • the catalyst composition mordeniteL (0.5 - 1.5 Macc%) / Zn (0.5 - 1.5 mass%) was used in the process of isomerization of n-butane at a temperature of 550 ° C.
  • the achieved conversion was in a satisfactory range of 45 - 48%, however, the selectivity was low: the content (mol%) of isobutane in the resulting product mixture was about 17.0, while the content of the products of the cracking side reactions (Q + C2 + C3) is 33.0.
  • US 5658839 A 08.19.1997.
  • the isomerization catalyst based on mordenite of the general composition A1 2 Oz eolite (59-60 mass%) / P1 (0.1-1.0 Macc%) Pd (0-1.0 mass%) was studied in the process of isomerization of n-hexane ( 310 ° C, 20 atm).
  • the catalyst allowed to achieve 20.0 - 36.9 mass% of the conversion of n-hexane with high selectivity: the total yield of iso-hexanes was 19.8 mass% for the conversion of n-hexane 20.0 mass% and 36.5 mass% for the conversion of n -hexane 36.9 mass%.
  • the catalyst based on ⁇ zeolite is attractive from the point of view of the absence of expensive metals (platinum, palladium and others) in the composition, however, it is characterized by a low yield of iso-paraffins - not more than 31 mass% (400 ° C, 1 atm, feed: n-hexane) and rapid decontamination - coke deposition is more than 8.0 mass% with a process duration of 4.3 hours
  • a catalyst based on a modified ZSM-5 zeolite of the composition CsGeZSM-5 / Pt (l, 0 mass%) is described and tested in the process of reforming light naphtha.
  • the the catalyst allowed to increase the value of OCH by 27 points, reaching a value of 78 for the obtained reformate (525 ° C, 1 atm).
  • SAPO silicoaluminophosphates
  • the activity of zeolites for each type of catalytic reactions is completely determined by a complex set of unique properties, to which, primarily include acidity and porosity.
  • Acidity i.e. the nature, strength, and number of acid sites of a zeolite, and porosity, namely, the effective width and geometry of the channels, determine the specific activity and selectivity of the catalytic transformations occurring in the presence of this zeolite.
  • a competing side process during catalytic isomerization is catalytic cracking, which inevitably leads to undesirable hydrocarbon losses due to the formation of low-value C 1 -C4 gases.
  • Both the target isomerization reaction and the side cracking reaction proceed with the participation of the acid centers of zeolites.
  • the excessively low acidity of zeolites will lead to a decrease in the proportion of the target isomerization reaction, while the increased acidity of zeolites will lead to an intensification of the side cracking reaction.
  • silicoaluminophosphates are medium acid zeolites, and therefore do not require additional modification in order to reduce acidity (deposition of metals such as Zn, Cs, Ge and others).
  • the silicoaluminophosphates of the ATO, AEL, and AFO structures have a one-dimensional system of disjoint channels with predominantly average effective widths, which limits the depth of isomerization of n-alkanes, thereby preventing the formation of easily cracked highly branched isomers, and, as a result, avoids undesirable loss hydrocarbons for the formation of low-value C 1 -C4 gases.
  • silicoaluminophosphates Due to the combination of the listed properties of silicoaluminophosphates, these zeolites undoubtedly represent promising objects of research in the framework of creating a catalyst with increased isomerizing activity for the reforming process.
  • the potential of silicoaluminophosphates as components of isomerization catalysts is not limited by the use of individual SAPO zeolites, but also consists in combining SAPO zeolites of various structures and combining SAPO zeolites with aluminosilicates in the composition of the catalyst.
  • the technical task of the invention is to develop a catalyst with increased isomerizing activity, containing not more than 0.3 wt% platinum and allowing efficient isomerization of alkanes of normal structure (n-alkanes) in the process of reforming hydrotreated gasoline fractions.
  • the technical result from the implementation of the claimed group of inventions is to increase the efficiency of isomerization of n-alkanes in the reforming process of hydrotreated gasoline fractions and to achieve a selectivity of formation of isomeric alkanes (iso-alkanes) of not less than 92.0 mass% with an increase in the content of iso-alkanes in reformate (stabilized catalysis) ) not less than 14.0 mass% relative to raw materials.
  • the catalyst according to the first embodiment contains platinum and tin deposited on a carrier containing silicoaluminophosphate zeolite SAPO-31 or silicoaluminophosphate zeolite SAPO-11 with the following content of components, wt.%:
  • the catalyst according to the second embodiment contains platinum deposited on a carrier containing a mixture of silicoaluminophosphate zeolite SAPO-31 and silicoaluminophosphate zeolite SAPO-11 with the following components, wt.%:
  • platinum (10.0-60.0 mass%) is successively applied to the carrier by cation exchange from an aqueous solution of platinum ammonia (Pt (NH 3 ) 4 Cl 2 ) or by impregnation from an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) and tin (0.07-0.30 mass%)
  • platinum ammonia Pt (NH 3 ) 4 Cl 2
  • H 2 PtCl 6 hexachloroplatinic acid
  • Example 1 The invention is illustrated, but not limited to, by the following examples.
  • Example 1 The invention is illustrated, but not limited to, by the following examples.
  • the preparation of catalyst Ns 1 is carried out by synthesis of a carrier comprising 10 mass% of silicoaluminophosphate zeolite S APO-31 and alumina, and subsequent sequential deposition of 0.3 mass% of platinum onto the carrier by cation exchange from an aqueous solution of platinum ammonia (Pt (NH 3 ) 4 Cl 2 ) and 0.20 mass% tin by impregnation by moisture absorption from a solution of SnCl 4 x 5H 2 0 in a mixture of concentrated hydrochloric acid (37 mass%) and distilled water.
  • a carrier comprising 10 mass% of silicoaluminophosphate zeolite S APO-31 and alumina
  • platinum ammonia Pt (NH 3 ) 4 Cl 2
  • 0.20 mass% tin platinum ammonia
  • the preparation of catalyst N ° 1 includes the following stages:
  • the resulting paste is molded using a piston extruder with a die of 1.5 mm diameter.
  • the resulting extrudates are dried at room temperature for 15 hours, dried in a drying oven with a stepwise rise in temperature (60, 80, PO ° C) and holding at each temperature for 3, 3 and 2 hours, respectively.
  • the dried extrudates are then broken into granules 1.5 to 2.5 mm long.
  • the obtained granules of the carrier are gradually heated for 10 hours in a muffle furnace to a temperature of 550 ° C and calcined at this temperature for 10 hours with a constant supply of air.
  • a solution is prepared by mixing 26.0 ml of distilled water, 37.5 ml of an aqueous solution of Pt (NH 3 ) 4 Cl2 with a concentration of 2.23 mg Pt ml and 2.7 ml of aqueous (25 wt% ) YSCHEN.
  • the solution is decanted, and the resulting catalyst is dried in an oven with a stepwise rise in temperature (60, 80, PO ° ⁇ ) and holding at each temperature for 3, 3 and 2 hours, respectively.
  • the dried granules of the catalyst are gradually heated for 24 hours in a muffle furnace to a temperature of 500 ° C and calcined at this temperature for 3 hours with a constant supply of air.
  • An impregnation solution is prepared by completely dissolving 0.061 g of SnCLjxStfeO (99.8 mass% of the basic substance) in a mixture of 0.23 ml of concentrated (37 mass%) hydrochloric acid and distilled water, with a total volume of 8.61 ml.
  • the resulting catalyst is dried in an oven with a stepwise rise in temperature (60, 80, 110 ° C) and holding at each temperature for 3, 3 and 2 hours, respectively.
  • catalyst N ° 2 The preparation of catalyst N ° 2 is carried out similarly to the catalyst Ne 1, the preparation of which is described in Example 1, except that the content of silicoaluminophosphate zeolite SAPO-31 is 40 mass%, after applying platinum to the dried and calcined at a temperature of 500 ° C, the catalyst granules are applied 0 , 07 mass% of tin.
  • catalyst ⁇ »3 is carried out similarly to the catalyst ⁇ ° 2, the preparation of which is described in Example 2, except that the carrier contains 10 mass% (5.28 g) of silicoaluminophosphate zeolite SAPO-11 instead of silicoaluminophosphate zeolite S APO-31.
  • catalyst ⁇ ° 4 is carried out similarly to the catalyst ⁇ ° 2, the preparation of which is described in Example 2, except that the carrier contains 60 wt% (31.70 g) of a mixture of silicoaluminophosphate zeolite S APO-31 and silicoaluminophosphate zeolite SAPO-11 instead of silicoaluminophosphate zeolite SAPO-31.
  • Example 5 The preparation of catalyst N ° 5 is carried out similarly to the catalyst N ° 2, the preparation of which is described in Example 2, except that 0.1 mass% of platinum is applied to the support.
  • catalyst ⁇ ° 6 is carried out similarly to the catalyst JN ° 4, the preparation of which is described in Example 4, except that the finished catalyst does not contain tin.
  • catalyst N ° 7 is carried out similarly to the catalyst N ° 2, the preparation of which is described in Example 2, except that the content of silicoaluminophosphate zeolite SAPO-31 is 60 mass%, after applying platinum to the dried and calcined at a temperature of 500 ° C, the catalyst granules are applied 0.30 mass% of tin.
  • catalyst N ° 8 is carried out similarly to the M 7 catalyst, the preparation of which is described in Example 7, except that the support additionally contains 10 wt% zeolite of the FAU structure (5.28 g of USY aluminosilicate in H * form with a molar ratio S1O2 / AI2O3 equal to 82.6), the finished catalyst does not contain tin.
  • catalyst ⁇ ° 9 is carried out similarly to the catalyst ⁇ ° 8, the preparation of which is described in Example 8, except that the carrier contains 15 wt.% Silicoaluminophosphate zeolite SAPO-11 instead of 40 wt.% Silicoaluminophosphate zeolite SAPO-31, the carrier additionally contains 60 wt.% FAU structure zeolite (USY 31.68 g of aluminosilicate in H * form with a molar ratio S1O2 / AI2O3 equal 82.6), application of platinum on a support formed by impregnation of an aqueous solution of hexachloroplatinic acid (KUCHSL b), after the application of platinum to the dried d catalyst applied Anulov 0.10 wt% tin ⁇ ° similarly to Catalyst 1, the preparation of which is described in Example 1.
  • the carrier contains 15 wt.% Silicoaluminophosphate zeolite SAPO-11 instead of 40 wt.%
  • the application of platinum on a carrier by impregnation from an aqueous solution of hexachloroplatinic acid involves the following steps: 1. Prepare an impregnation solution by mixing 29.7 ml of distilled water, 3.03 ml of an aqueous solution of H 2 P1: C1 b with a concentration of 11.30 mg Pt / ml, 0.13 ml of concentrated (37 mass%) hydrochloric acid and 0 , 16 ml of “glacial” acetic acid.
  • the solution is decanted, the resulting catalyst is dried in an oven with a stepwise rise in temperature (60, 80, 110 ° ⁇ ) and holding at each temperature for 3, 3 and 2 hours, respectively.
  • the preparation of the catalyst Jfe 10 is carried out similarly to the catalyst ⁇ ° 9, the preparation of which is described in Example 9, except that the carrier contains 40 wt.% A mixture of silicoaluminophosphate zeolite SAPO-31 and silicoaluminophosphate zeolite SAPO-11 instead of 15 wt.% Silicoaluminophosphate zeolite S APO-11 , the finished catalyst does not contain tin and zeolite structure FAU.
  • catalyst JV 11 is carried out similarly to catalyst N ° 10, the preparation of which is described in Example 10, except that the content of the mixture of silicoaluminophosphate zeolite SAPO-31 and silicoaluminophosphate zeolite S APO-11 is 10 mass%, the carrier additionally contains 10 mass% of the zeolite structure FAU, after applying platinum to the dried granules of the catalyst, 0.10 mass% of tin is applied, similarly to the catalyst N ° 1, the preparation of which is described in Example 1.
  • composition of the claimed catalyst samples based on zeolites of the ATO or / and AEL structure silicoaluminophosphate zeolite SAPO-31 or silicoaluminophosphate zeolite S APO-11 or a mixture of silicoaluminophosphate zeolite SAPO-31 and silicoaluminophosphate zeolite SAPO-11.
  • the composition of the catalyst comparison.
  • the catalysts N ° 1-11, prepared by the method described in Examples 1-11, respectively, and the comparison catalyst were tested in the process of low-temperature reforming carried out in a flow catalytic installation.
  • This installation is equipped with a heated casing in which gas and liquid lines, a mixer, and a reactor are placed.
  • the inner diameter of the reactor is 1.3 cm, the volume of the loaded catalyst is 10 cm 3 .
  • raw materials from a container located on an electronic scale are fed into the system by a high-pressure plunger pump.
  • the exact mass of the feed is recorded based on the readings of the electronic balance.
  • the raw material enters the mixer, where it is mixed with hydrogen, the reaction mixture enters the reactor.
  • the resulting products are discharged from the bottom of the reactor and sent to a separator, where the gas phase (hydrogen-containing gas) is separated from liquid catalysis.
  • Liquid catalyzate from the separator enters the refrigerator-sampler, cooled to -10 ° C with antifreeze, continuously circulating through the “jacket” of the apparatus. Periodic sampling of liquid catalysis is carried out from the refrigerator-sampler for analysis.
  • the developed catalyst based on silicoaluminophosphate zeolite of the ATO or / and AEL structure is characterized by a platinum content of not more than 0.3 mass% and provides:
  • the resulting catalyst based on silicoaluminophosphate zeolites of the ATO or / and AEL structure is significantly more effective than the platinum-rhenium comparison catalyst within all three of the above parameters at process temperatures not exceeding 380 ° C (Tables 3 and 4).
  • the total content of expensive active metals platinum and rhenium is 0.6 mass%, which is more than 2 times the corresponding value (not more than 0.3 mass% Pt) for the claimed catalyst (Table 2).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Le groupe d'invention concerne un catalyseur d'isomérisation de n-alcanes dans un processus de reformage de fractions d'essence hydro-purifiées. Selon une première variante, le catalyseur comprend, en % en poids: platine 0,1-0,3, étain 0,07-0,30, zéolite à base de silicoaluminophosphate SAPO-31 ou zéolite à base de silicoaluminophosphate SAPO-11 10-60, le reste se composant d'oxyde d'aluminium. La plupart du temps, le catalyseur comprend en outre de la zéolite à structure FAU dans une quantité de 10,0-60,0 % en poids, et on utilise en qualité de zéolite à structure FAU de l'aluminosilicate sous forme H+ selon un rapport molaire SiO2/Al2O3 égal à 82,6. Selon une seconde variante comprend en % en poids: platine 0,1-0,3, un mlange de zéolite à base de silicoaluminophosphate SAPO-31 et de zéolite à base de silicoaluminophosphate SAPO-11 10,0-60,0, le reste se composant d'oxyde d'aluminium. La plupart du temps, le catalyseur comprend en outre de la zéolite à structure FAU dans une quantité de 10,0-60,0 % en poids, et on utilise en qualité de zéolite à structure FAU de l'aluminosilicate sous forme H+ selon un rapport molaire SiO2/Al2O3 égal à 82,6, et de l'étain dans une quantité de 0,1-0,30 % en poids. L'invention permet d'effectuer efficacement une isomérisation de n-alcanes dans un processus de de reformage de fractions d'essence hydro-purifiées, tout en garantissant une sélectivité de formation d'iso-alcanes d'au moins 92% en poids et une augmentation du contenu en iso-alcanes dans produit de reformage (produit de catalyse stabilisé) d'u moins 14 % en poids par rapport à la matière première.
PCT/RU2017/000666 2016-09-16 2017-09-13 Catalyseur d'isomérisation de n-alcanes dans un processus de reformage de fractions d'essence hydro-purifiées (variantes) WO2018052341A1 (fr)

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RU2016137134A RU2626747C1 (ru) 2016-09-16 2016-09-16 Катализатор изомеризации н-алканов в процессе риформинга гидроочищенных бензиновых фракций (варианты)
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Cited By (1)

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CN114602548A (zh) * 2022-01-24 2022-06-10 中国科学院上海高等研究院 一种金属单原子分散的烷烃异构化催化剂及其制备方法

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US4417083A (en) * 1980-05-09 1983-11-22 Elf France Process for the dehydrocyclization of paraffins at low pressure
CN1283668A (zh) * 1999-07-06 2001-02-14 中国石油化工集团公司 一种烷烃临氢异构化催化剂
RU2257954C1 (ru) * 2004-05-12 2005-08-10 Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук Способ приготовления катализатора и способ изомеризации н- парафинов с использованием этого катализатора
US20100317910A1 (en) * 2009-06-12 2010-12-16 Albemarle Europe Sprl Sapo molecular sieve catalysts and their preparation and uses

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US6596156B1 (en) * 2001-01-05 2003-07-22 China Petroleum And Chemical Corporation SAPO-11 molecular sieve, its synthetic method and a catalyst containing the molecular sieve
RU2248342C1 (ru) * 2003-12-29 2005-03-20 Московская государственная академия тонкой химической технологии им. М.В. Ломоносова Способ получения высокооктановой добавки бензина

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US4417083A (en) * 1980-05-09 1983-11-22 Elf France Process for the dehydrocyclization of paraffins at low pressure
CN1283668A (zh) * 1999-07-06 2001-02-14 中国石油化工集团公司 一种烷烃临氢异构化催化剂
RU2257954C1 (ru) * 2004-05-12 2005-08-10 Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук Способ приготовления катализатора и способ изомеризации н- парафинов с использованием этого катализатора
US20100317910A1 (en) * 2009-06-12 2010-12-16 Albemarle Europe Sprl Sapo molecular sieve catalysts and their preparation and uses

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114602548A (zh) * 2022-01-24 2022-06-10 中国科学院上海高等研究院 一种金属单原子分散的烷烃异构化催化剂及其制备方法
CN114602548B (zh) * 2022-01-24 2023-05-23 中国科学院上海高等研究院 一种金属单原子分散的烷烃异构化催化剂及其制备方法

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