WO2001023085A1 - Catalyseur destine a la deshydrogenation d'hydrocarbures et procede de fabrication correspondant - Google Patents

Catalyseur destine a la deshydrogenation d'hydrocarbures et procede de fabrication correspondant Download PDF

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Publication number
WO2001023085A1
WO2001023085A1 PCT/RU2000/000351 RU0000351W WO0123085A1 WO 2001023085 A1 WO2001023085 A1 WO 2001023085A1 RU 0000351 W RU0000351 W RU 0000351W WO 0123085 A1 WO0123085 A1 WO 0123085A1
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WO
WIPO (PCT)
Prior art keywords
aluminum
metal
alkaline
catalyst
οκsid
Prior art date
Application number
PCT/RU2000/000351
Other languages
English (en)
Russian (ru)
Inventor
Tatiyana Vladimirovna Borisova
Alexandr Vasilievich Kachkin
Mikhail Grigorievich Makarenko
Olga Mikhailovna Melnikova
Valery Vasilievich Sotnikov
Original Assignee
Zakrytoe Aktsionernoe Obschestvo 'katalizatornaya Kompaniya'
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 Zakrytoe Aktsionernoe Obschestvo 'katalizatornaya Kompaniya' filed Critical Zakrytoe Aktsionernoe Obschestvo 'katalizatornaya Kompaniya'
Priority to AU70447/00A priority Critical patent/AU7044700A/en
Publication of WO2001023085A1 publication Critical patent/WO2001023085A1/fr

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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • 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
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina

Definitions

  • the invention is available for the use of catalysts for the dehydration of various carbohydrates, in particular for the dehydration of 2 gases.
  • the predominant olefin level is one of the most important products of the urban synthesis. They are used in the manufacture of polypropylenes, high-quality additives (methyl-blended ether) of gasoline and a whole range of industrial gases.
  • One of the methods of receiving olefins is the dehydration of paraffins. It is well known that with thermodynamic vision, dehydration of hydrocarbons C 2 -C 5 is not affected by the number of effective processes. Such a reaction of dehydration is endothermic, in order to achieve a technically acceptable inversion of raw materials, a temperature of 500-600 ° C is necessary. However, at this point, there are 5 treatments with a noticeable speed that prevent undesired good-bye reactions to measurement and measurement.
  • the catalyzed process of dehydration should direct the process to an energetically disadvantageous path. ⁇ . e. To allow the process to exist and to lower the temperature of the ground, and to make the speed of the reaction of the crushing to a minimum possible. By doing so, it must minimize the inevitable development of a certain amount of coal and non-cash property. To prevent the dehydration of catalyzed substances, it is necessary to ensure a high selectivity for the desired reduction in the amount of waste water.
  • ⁇ ig ⁇ vleniya ⁇ a ⁇ aliza ⁇ a is ⁇ lzuyu ⁇ n ⁇ si ⁇ el - aluminum ⁇ sid as ⁇ able ⁇ , ⁇ i ⁇ yvayu ⁇ n ⁇ si ⁇ el ⁇ as ⁇ v ⁇ m, s ⁇ de ⁇ zhaschim s ⁇ edineniya ⁇ ma and tsi ⁇ niya, ⁇ sle ⁇ i ⁇ i ⁇ du ⁇ susha ⁇ in va ⁇ uume, za ⁇ em ⁇ v ⁇ dya ⁇ ⁇ e ⁇ - 0 m ⁇ b ⁇ ab ⁇ u ⁇ i 740 ° C, za ⁇ em ⁇ susches ⁇ vlyayu ⁇ ⁇ i ⁇ u ⁇ a ⁇ aliza ⁇ a s ⁇ edineniem schel ⁇ chn ⁇ g ⁇ or schel ⁇ chn ⁇ zemeln ⁇ g ⁇ me ⁇ alla and two-stage drying, first in a vacuum, then in the air, then the process is heated at 740
  • the system has an increased service cycle due to the reduction of the 5th title of the cash register, but the method of its receipt is also monitored and has a lot of consequences.
  • the catalyst was known to be available for the dehydration of ethylbenzene in the building (Application no. 885654, ⁇ P ⁇ ⁇ ShZ / 26, ⁇ 07 ⁇ 5 / 333, 1998), and also for the delivery of Carbon, 21 Oct.
  • the sample at a minimum of 5 ° C is operated at a temperature of 450 ° C, and then at a temperature of 1,030 ° C, it is improved a composite crystalline structure consisting of delta, theta, delta and theta, theta and alpha, or the delta, theta and alpha.
  • the carrier obtained in this way is fed with the components of the catalyst and then turned off at the temperature of 750 ° ⁇ .
  • the proposed catalytic converter is designed to increase the yield of olefins, but the problem with the catalytic converter is that it is inaccessible to a small amount of electricity.
  • the method of catalysing is compiled.
  • ⁇ a ⁇ im ⁇ b ⁇ az ⁇ m in izves ⁇ ny ⁇ ⁇ e ⁇ niches ⁇ i ⁇ ⁇ esheniya ⁇ for ⁇ ig ⁇ vleniya ⁇ ms ⁇ de ⁇ zhaschi ⁇ ⁇ a ⁇ aliza ⁇ v is ⁇ lzuyu ⁇ n ⁇ si ⁇ el having s ⁇ mi ⁇ van- hydrochloric ⁇ is ⁇ alliches ⁇ uyu s ⁇ u ⁇ u ⁇ u (gamma ⁇ sid aluminum del ⁇ a, ⁇ e ⁇ a and d ⁇ .), ⁇ - ⁇ y ⁇ i ⁇ yvayu ⁇ ⁇ m ⁇ nen ⁇ ami ⁇ a ⁇ aliza ⁇ v izves ⁇ nymi me ⁇ dami with ⁇ sle- blowing ⁇ e ⁇ m ⁇ b ⁇ ab ⁇ y.
  • the obtained catalysts have a lack of availability, and there is a problem with the simple connection of the circuits to the supply of power and is inadequate.
  • the compound of the modifying metal from the group: ⁇ , ⁇ , ⁇ réelle, ⁇ réelle, ⁇ , ⁇ , ⁇ or their mixture 0.1-5 5
  • Aluminum oxide, external. 0 The components of the catalytic converter are equally distributed in aluminum oxide and have an X-ray structure.
  • ⁇ izves ⁇ ny ⁇ ⁇ esheniya ⁇ for ⁇ ig ⁇ vleniya ⁇ ms ⁇ de ⁇ zhascheg ⁇ ⁇ a ⁇ aliza ⁇ a degid ⁇ i ⁇ vaniya uglev ⁇ d ⁇ d ⁇ v is ⁇ lzuyu ⁇ n ⁇ si ⁇ el having s ⁇ mi ⁇ - bathroom ⁇ is ⁇ alliches ⁇ uyu s ⁇ u ⁇ u ⁇ u (gamma- ⁇ 1 ⁇ 3> ⁇ e ⁇ a, del ⁇ a and d ⁇ .)
  • the X-ray composition of the components of the catalytic converter is preferable for ensuring the increased activity of the catalyst.
  • d ⁇ bav ⁇ i as s ⁇ edineny neme ⁇ all ⁇ v, b ⁇ a and / or ⁇ emniya in ⁇ liches ⁇ ve 0.01-10% by weight and me ⁇ all ⁇ v - ⁇ dn ⁇ g ⁇ or mixtures of vyb ⁇ anny ⁇ g ⁇ u ⁇ y: tsi ⁇ ny, ⁇ i ⁇ an , iron, gallium, flint, molybdenum, manganese, tin in a quantity of 0.1-5% by weight
  • the size and volume of the particles of the catalyst are controlled by the conditions for the dehydration process.
  • catalysts are supplied with a special type of particles with a quick and easy process. Larger, quicker particle transfer results in a better mass transfer than smooth particle transfer.
  • the standardization for a stationary unit may be made in the form of a granule of a different shape, for example, a size of 4 x 4 mm.
  • the proposed method makes it possible to significantly reduce the cost of obtaining dehydration catalysts compared to the existing ones.
  • ⁇ a ⁇ ig. 3, 4 are presented photographs of the particles of the catalytic converter at various magnifications.
  • ⁇ a ⁇ ig. 3 increase of 600 ⁇ az
  • ⁇ ig. 4 increase in 2000 ⁇ az.
  • the particles of the catalytic converter are not equipped with a standard for connecting 5 aluminum ⁇ 1 ⁇ 3 • ⁇ ⁇ 2 ⁇ , where ⁇ was found to be
  • This compound can be obtained by any known means, for example, by quick dehydration of a hydraulic
  • the hydrosol of the region is used, which is a sysilane.
  • a disinfecting aluminum compound may also partially contain a brown compound, and a missing amount of brown enters into the commercialization.
  • modular metals from the group: titanium, titanium, iron, gallium, calcium, molybdenum, manganese, are used in the food industry.
  • the implements are simultaneously or indirectly processed by all the components of the catalyst by any known method.
  • the preferred method is the application of all components for moisture absorption, ⁇ . ⁇ . There is no waste water that contains foreign compounds in the house.
  • the separation of the components of the materials used in the technology of the preparation of the dehydration catalyst for the sale of radiophysics is the basis for the production of radiophysical products.
  • Inventory is allocated to the mass market until the end of the catalytic converter.
  • the method is based on the destruction of particles in the catalytic converter and the measurement of the mass of particles carried away by direct air flow, so that the speed of the process is stabilized.
  • the dried catalytic converter dry in a vacuum.
  • the dried catalytic converter calcines at 700 ° ⁇ .
  • the product is similar in type 1, only the aluminum connection is broken, and the unit is non-compliant
  • the aluminum compounds and modifying compounds are given in table ⁇ ° 1, and the properties of the obtained catalysts are in table ⁇ ° 2.
  • the resulting spherical catalytic system has components and properties, 5 presented in tables ⁇ ° ⁇ ° 1 and 2. 12
  • Example 9 It is prepared for the same procedure as in Example 6, since it is only a little different. All data are given in the table ⁇ ° ⁇ ° 1 and 2.
  • the proposed catalysts and methods for its preparation can be used in chemical industry for the dehydration of hydrocarbons, for example, butane has been tested, butane has been removed from it.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un catalyseur à chrome destiné à la déshydrogénation d'hydrocarbures et un procédé de fabrication de ce catalyseur. Le catalyseur possède une structure dans laquelle l'oxyde d'aluminium possède un réseau cristallin défectueux avec une distance interfaciale d440=1,41-1,43 Å, les composants du catalyseur (constitués de chrome, d'un métal alcalin et/ou alcalino-terreux, d'un métal modificateur du groupe comprenant le zircone, le titan, le fer, le gallium, le cobalt, le molybdène, le manganèse et l'étain, ainsi qu'un non-métal tel que le bore et/ou le silicium) sont répartis à égalité dans l'oxyde d'aluminium et possèdent une structure amorphe sous les rayons X. Le catalyseur possédant cette structure et cette composition présente une dureté plus élevée, un plus grand degré d'activité et de sélectivité; il est obtenu par le trempage du composé d'aluminium, qui a une structure stratifiée amorphe sous les rayons X correspondant à la formule Al2O3*nH2O dans laquelle n=0,3-1,5, dans des composés de composants du catalyseur, ledit trempage étant suivi d'une calcination à une température de 700-800 °C.
PCT/RU2000/000351 1999-09-28 2000-08-31 Catalyseur destine a la deshydrogenation d'hydrocarbures et procede de fabrication correspondant WO2001023085A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU70447/00A AU7044700A (en) 1999-09-28 2000-08-31 Catalyst for hydrocarbon dehydrogenation and method therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU99120302 1999-09-28
RU99120302/04A RU2148430C1 (ru) 1999-09-28 1999-09-28 Катализатор для дегидрирования углеводородов и способ его получения

Publications (1)

Publication Number Publication Date
WO2001023085A1 true WO2001023085A1 (fr) 2001-04-05

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AU (1) AU7044700A (fr)
RU (2) RU2148430C1 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1024738C2 (nl) * 2002-11-08 2005-02-23 Sued Chemie Inc Gefluïdiseerd-bedkatalysator voor de dehydrogenatie van koolwaterstoffen.

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104209123B (zh) * 2014-08-11 2017-03-29 中海油天津化工研究设计院有限公司 一种含银和硼低碳烷烃脱氢催化剂及其制备方法
RU2627667C1 (ru) * 2016-11-30 2017-08-09 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ, НИ ТГУ) Катализатор с низким содержанием оксида хрома для дегидрирования изобутана и способ дегидрирования изобутана с его использованием
RU2698308C1 (ru) * 2019-06-24 2019-08-26 Общество С Ограниченной Ответственностью "Научно-Производственная Компания "Синтез" Катализатор для дегидрирования парафиновых с3-с5 углеводородов
RU2735920C1 (ru) * 2020-02-26 2020-11-10 Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" Катализатор для дегидрирования парафиновых углеводородов и способ его приготовления
US20240139714A1 (en) * 2022-02-07 2024-05-02 Dmitry Aleksandrovich ANASHKIN Hydrocarbons dehydrogenation catalyst (variants)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2162082A (en) * 1984-07-25 1986-01-29 Air Prod & Chem Improved catalyst for hydrocarbon dehydrogenation
US4746643A (en) * 1985-06-17 1988-05-24 Snamprogetti S.P.A. Method for the preparation of a catalyst for the dehydrogenation of C3 -C5 paraffins
DE4422770A1 (de) * 1994-06-29 1996-01-04 Basf Ag Katalysator und Verfahren für die katalytische oxidative Dehydrierung von Alkylaromaten und Paraffinen
US5489722A (en) * 1992-04-27 1996-02-06 Sun Company, Inc. (R&M) Dehydrogenation processes using catalysts comprising catalytic metal on a nonacidic support

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2162082A (en) * 1984-07-25 1986-01-29 Air Prod & Chem Improved catalyst for hydrocarbon dehydrogenation
US4746643A (en) * 1985-06-17 1988-05-24 Snamprogetti S.P.A. Method for the preparation of a catalyst for the dehydrogenation of C3 -C5 paraffins
US5489722A (en) * 1992-04-27 1996-02-06 Sun Company, Inc. (R&M) Dehydrogenation processes using catalysts comprising catalytic metal on a nonacidic support
DE4422770A1 (de) * 1994-06-29 1996-01-04 Basf Ag Katalysator und Verfahren für die katalytische oxidative Dehydrierung von Alkylaromaten und Paraffinen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1024738C2 (nl) * 2002-11-08 2005-02-23 Sued Chemie Inc Gefluïdiseerd-bedkatalysator voor de dehydrogenatie van koolwaterstoffen.

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Publication number Publication date
RU2287366C1 (ru) 2006-11-20
AU7044700A (en) 2001-04-30
RU2148430C1 (ru) 2000-05-10

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