SU490278A3 - The method of obtaining silver catalyst - Google Patents

The method of obtaining silver catalyst

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Publication number
SU490278A3
SU490278A3 SU1719711A SU1719711A SU490278A3 SU 490278 A3 SU490278 A3 SU 490278A3 SU 1719711 A SU1719711 A SU 1719711A SU 1719711 A SU1719711 A SU 1719711A SU 490278 A3 SU490278 A3 SU 490278A3
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USSR - Soviet Union
Prior art keywords
silver
ethanolamine
solution
ethylene
mol
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SU1719711A
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Russian (ru)
Inventor
Петер Ниельсен Роберт
Original Assignee
Шел Интернэшнл Рисерч Маатсхаппий Н.В. (Фирма)
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Application filed by Шел Интернэшнл Рисерч Маатсхаппий Н.В. (Фирма) filed Critical Шел Интернэшнл Рисерч Маатсхаппий Н.В. (Фирма)
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48Silver or gold
    • B01J23/50Silver
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/02Synthesis of the oxirane ring
    • C07D301/03Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • C07D301/10Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold

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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)
  • Epoxy Compounds (AREA)

Description

4 Таблица 14 Table 1

НосительCarrier

Примечание: В том числе 0,27 вес. %- окиси бари .Note: Including 0.27 wt. % - barium oxide.

Растворы дл  приготовлени  катализаторов готов т следующим образом.Solutions for the preparation of catalysts are prepared as follows.

I. Оксалат серебра, аммиак, этаноламирг. Свежеприготовленный осадок щавелевокислого серебра из водных растворов азотнокислогоI. Silver oxalate, ammonia, ethanolamine. Freshly prepared silver oxalate precipitate from aqueous solutions of nitrate

серебра и щавелевокислого кали  (соли соответствуют но степени чистоты категории ч.д.а.) 25 п тикратно промывают деионизировавдиой водой , затем раствор ют в водном растворе аммиака с концентрацией 30 вес. %, что привоТ а б л д ц а 2silver and potassium oxalate (salts correspond to the degree of purity of the category chd) 25 times washed with deionized water, then dissolved in an aqueous solution of ammonia with a concentration of 30 wt. % that privot a b d d c a 2

дит к получению раствора А§{КНз)2 2С2О4 L концентрацией 1,43 мол. %. В заключение этот раствор смешивают с этаноламином с таким расчетом, чтобы его концентраци  составила 10 об. %, что соответствует, примерно, содержанию около 0,5 моль этаноламина на 1 моль серебра.It leads to the preparation of a solution of Ag (KNZ) 2 2C2O4 L with a concentration of 1.43 mol. % In conclusion, this solution is mixed with ethanolamine in such a way that its concentration is 10 vol. %, which corresponds approximately to the content of about 0.5 mol of ethanolamine per 1 mol of silver.

Л. Оксилат серебра, аммиак, этаноламин. Поступают как указано в случае получени  раствора 1 с тем отличием, что мол рное соотношение между серебром и этаноламином равно 1:1.L. Oxylate silver, ammonia, ethanolamine. Proceed as indicated in the preparation of solution 1 with the difference that the molar ratio between silver and ethanolamine is 1: 1.

III.Оксалат серебра, аммиак, этаноламин. Поступают как указано в случае получени  раствора I с тем отличием, что мол рное соотношение между серебром и этаноламином равно 1:1,5.III.Oxalate silver, ammonia, ethanolamine. Proceed as indicated in the preparation of solution I with the difference that the molar ratio between silver and ethanolamine is 1: 1.5.

IV.Оксалат серебра, аммиак, этаноламин. Поступают, как указано в случае получени  -раствора I с тем отличием, что мол рное соотношение между серебром и этаноламином равно 1:2.IV.Oxalate silver, ammonia, ethanolamine. Proceed as indicated in the case of preparation of solution I with the difference that the molar ratio between silver and ethanolamine is 1: 2.

V.Оксалат серебра, этилендиамин, этано .ламин. Чистый раствор оксалата серебра, приготовленный как указано дл  случа  раствора I, раствор ют в водном растворе, содержащем 4,2 моль/л этилендиамина (ЭН) с -таким .расчетом, чтобы получать раствор, содержаш ,ий 2,05 моль (Ag23H)C2O4 на 1 л. Затем к этому раствору. Так жекак в случае раствора I, добавл ют этаноламин в количестве 10 об. %.V. Silver oxalate, ethylenediamine, ethano. Alamine. A pure solution of silver oxalate, prepared as indicated for solution I, is dissolved in an aqueous solution containing 4.2 mol / L of ethylenediamine (EN) with the same calculation, to obtain a solution containing 2.05 mol (Ag23H) C2O4 to 1 l. Then to this solution. Also, in the case of solution I, ethanolamine is added in an amount of 10 vol. %

VI.Карбонат серебра, этилендиамин, этаноламин . Карбонат серебра раствор ют в водном растворе этилендиамина с таким расче-том , чтобы получать раствор, содержаш.ий 4,5 моль серебра на 1 л. Причем получено мо .лекул рное соотношение между этилендиамином и серебром, наход щеес  в пределах -1,2-1,1. Затем добавл ют 0,4 моль этанолами ,на на 1 моль серебра. Готовый раствор содер:жал 4,0 моль серебра на 1 л.VI. Silver carbonate, ethylenediamine, ethanolamine. Silver carbonate is dissolved in an aqueous solution of ethylene diamine in such a way as to obtain a solution containing 4.5 moles of silver per liter. Moreover, a molecular ratio between ethylenediamine and silver was obtained, ranging from -1.2-1.1. Then 0.4 mol of ethanol is added per 1 mol of silver. The prepared solution contained: sting 4.0 mol of silver per 1 liter.

VII.Молочнокислое серебро, этилендиамин, -этаноламин.VII.Lactic silver, ethylene diamine, ethanolamine.

VIII.Уксуснокислое серебро, этилендиамин , этаноламин.VIII. Acetic silver, ethylenediamine, ethanolamine.

IX.Глюцинат серебра, этилендиамин, эта:Ноламин .IX.Glucinate silver, ethylenediamine, this: Nolamin.

X.Лимоннокислое серебро, этилендиамин, -этаноламин.X. Sodium silver, ethylene diamine, ethanolamine.

Растворы VII-X получали, как и раствор VI, замен ли лишь серебр ную соль.Solutions VII-X were obtained, like solution VI, only the silver salt was replaced.

XI.Щавелевокислое серебро, аммиак, эти .лендиамин. Метод получени  тот же, что и дл XI.Silberic silver, ammonia, these .lenediamine. The method of obtaining is the same as for

раствора I, но вместо 10 об. % этаноламина примен ли 10 вес. % этилендиамина.solution I, but instead of 10 vol. % ethanolamine used 10 wt. % ethylenediamine.

У предлагаемых катализаторов серебро на-ходитс  в виде почти полукруглых частиц, ко-торые равномерно распределены по поверхности . Частицы серебра особенно крепко скреплены с поверхностью, как при повторных свободных падени х и встр хивании.In the proposed catalysts, silver is in the form of almost semicircular particles, which are uniformly distributed over the surface. Silver particles are especially strongly bonded to the surface, as with repeated free falls and shaking.

Пример 2. Сравнение катализаторов в ;случае получени  окиси этилена в их присут ,ствии.Example 2. Comparison of catalysts in the case of the preparation of ethylene oxide in their presence.

Все катализаторы, приведенные в примере 1, испытаны в отношении применени  дл  синтеза окиси этилена в промышленных услови х .All catalysts described in Example 1 were tested for use in the synthesis of ethylene oxide under industrial conditions.

При проведении опытов, пр мое окисление этилена до окиси этилена посредством молекул рного кислорода осуществл ют в реакторе в виде единичной трубки в услови х однократного пропускани  реагирующих веществ (однопроходный метод). Однако подбирают состав газовой смеси таким образом, чтобь он соответствовал составу дл  крупных установок с системой рециркул ции. Пропускаема  газова  смесь максимально упрощена по составу и содержит этилен и воздух .In tests, the direct oxidation of ethylene to ethylene oxide by means of molecular oxygen is carried out in the reactor as a single tube under the conditions of a single pass of reactants (single pass method). However, the composition of the gas mixture is selected so that it corresponds to the composition for large installations with a recirculation system. The permeable gas mixture is maximally simplified in composition and contains ethylene and air.

Примен ема  трубка имеет столь малые размеры, что кольца размером 8X8 мм,, на которые нанесен катализатор, приходилось измельчать до размера частиц, проход щих через сито мёш. Трубка имела внутренний диаметр около 0,5 см и длину около 12,5 см. Ко.пичество нaxoд IцeгQc  в трубке катализатора составл ло 3,5 г; услови  проведени  реакции следующие:The tube used is so small that rings of size 8x8 mm, on which the catalyst was applied, had to be ground to the size of particles passing through a mesh of mesh. The tube had an internal diameter of about 0.5 cm and a length of about 12.5 cm. The amount of nitride in the catalyst tube was 3.5 g; The reaction conditions are as follows:

Давление, абс. атм15Pressure abs. atm15

Производительность, час2360Productivity, hour 2360

Содержание этилена в подаваемой смеси, мол. %30The ethylene content in the feed mixture, mol. %thirty

Соотношение между этиленом и кислородом в подаваемой смеси 3,751 Содерж:ание .хлора в составе подаваемой смеси, вес. части на млн. вес. ч.2Ratio between ethylene and oxygen in the feed mixture 3,751 Content: chlorine in the feed mixture, weight. parts per million by weight part 2

При оценке применимости катализаторов, в качестве важнейшего показател  принималась селективность образовани  окиси этилена как целевого продукта из прореагировавшего этилена или кислорода, обозначаемых далее, как S{Et) или S(O2).When assessing the applicability of catalysts, the selectivity of the formation of ethylene oxide as the target product from reacted ethylene or oxygen, hereinafter referred to as S {Et) or S (O2), was taken as the most important indicator.

Процентное замешение за один проход обозначено С (Et) и С (О2).Percentage mixing in a single pass is designated C (Et) and C (O2).

Процентные величины, характеризующие селективность, имеют различные значени . Объ сн етс  это тем, что непрореагировавшие вещества в практических услови х в преобладающем количестве возвращаютс  в зону реакции дл  повторного использовани  и таким путем дополнительно внос т свою долю при образовании целевого продукта.Percentages characterizing selectivity have different meanings. This is explained by the fact that, in practical terms, unreacted substances in the prevailing amount are returned to the reaction zone for reuse and thus contribute their share in the formation of the target product.

Величины S(Et) и S(O2), как и C(Et) и С(О2) взаимосв заны при заданном соотношении между этиленом и кислородом в составе подводимого газа.The values of S (Et) and S (O2), as well as C (Et) and C (O2), are interrelated for a given ratio between ethylene and oxygen in the composition of the supplied gas.

Замещение (конверси )  вл етс  величиной , определ ющей производственную мощность . В св зи с тем, что практически вс  образовавша с  окись этилена выдел етс  из состава реакционной смеси путем отмывки водой , количество окиси этилена, выработанное за 1 час, можно онределить следующим образом .Substitution (conversion) is the quantity that determines production capacity. Due to the fact that practically all the ethylene oxide formed is released from the composition of the reaction mixture by washing with water, the amount of ethylene oxide produced in 1 hour can be determined as follows.

Количество этилена, поступающее за 1 час в зону реакции, умножают наThe amount of ethylene entering the reaction zone in 1 hour is multiplied by

SU1719711A 1970-12-02 1971-11-30 The method of obtaining silver catalyst SU490278A3 (en)

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US9426970A 1970-12-02 1970-12-02
US9436670A 1970-12-02 1970-12-02

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SU1847494A SU540554A3 (en) 1970-12-02 1972-11-06 Silver catalyst for the oxidation of organic compounds

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JP (1) JPS5522146B1 (en)
AU (1) AU458053B2 (en)
BE (1) BE775697A (en)
CA (1) CA1004214A (en)
CH (1) CH587080A5 (en)
CS (1) CS191201B2 (en)
DD (1) DD96643A5 (en)
DE (1) DE2159346C3 (en)
FR (1) FR2117183A5 (en)
GB (1) GB1369639A (en)
IE (1) IE35857B1 (en)
IT (1) IT941880B (en)
NL (1) NL171237C (en)
NO (1) NO130419B (en)
SE (1) SE374279B (en)
SU (2) SU490278A3 (en)

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NL172326C (en) * 1972-12-15 1984-02-16 Shell Int Research PROCESS FOR PREPARING ETHYLENE OXIDE, PROCESS FOR PREPARING A CATALYST USED THEREIN, AND PRODUCTS FORMED, CONTAINING THIS CATALYST.
DE2418712C2 (en) * 1974-04-18 1982-07-29 Nižnetagil'skij zavod plastmass, Nižnij Tagil, Sverdlovskaja oblast' Process for the production of formaldehyde by the oxidation of methanol in the presence of a silver catalyst
GB1517608A (en) * 1975-12-29 1978-07-12 Texaco Development Corp Silver catalyst for ethylene epoxidation
US4097414A (en) * 1976-08-30 1978-06-27 Texaco Development Corp. Modified ethylene oxide catalyst and a process for its preparation
FR2432023A2 (en) * 1978-04-28 1980-02-22 Ugine Kuhlmann SILVER-BASED CATALYSTS FOR THE PRODUCTION OF ETHYLENE OXIDE
JPS57168253U (en) * 1981-04-18 1982-10-23
JPS5895665U (en) * 1981-12-23 1983-06-29 株式会社リコー Foto Katsupura
EP0172565B1 (en) * 1984-08-21 1991-03-13 Mitsubishi Petrochemical Co., Ltd. Silver catalyst for production of ethylene oxide from ethylene, and process for production thereof
JPS61114862U (en) * 1984-12-28 1986-07-19
DE3528313A1 (en) * 1985-08-07 1987-02-12 Basf Ag SILVER CATALYST, ITS PRODUCTION AND USE
JPH0678271B2 (en) * 1986-07-12 1994-10-05 三菱油化株式会社 Method for producing silver oxalate
DE59003342D1 (en) * 1989-11-09 1993-12-09 Huels Chemische Werke Ag Silver catalyst for the oxidation of ethylene and process for its production.
US5173469A (en) * 1989-11-09 1992-12-22 Huels Aktiengesellschaft Silver catalyst suitable for oxidation of ethylene and process for the production of the catalyst
DE3937247A1 (en) * 1989-11-09 1991-05-16 Huels Chemische Werke Ag Silver catalyst for oxidn. of ethylene to ethylene oxide - by pptn. of silver on porous, heat-resistant support so concn. of silver at surface is higher than inside particles
DE10131297A1 (en) 2001-06-29 2003-01-09 Basf Ag Production of partial (ammo)oxidation products of an olefinic hydrocarbon, useful for acrolein/acrylic acid from propane, comprises intermittent supplementation of olefin from another source.
DE10232482A1 (en) 2002-07-17 2004-01-29 Basf Ag Process for the safe operation of a continuous heterogeneously catalyzed gas phase partial oxidation of at least one organic compound
US7115776B2 (en) 2002-07-18 2006-10-03 Basf Aktiengesellschaft Heterogeneously catalyzed gas-phase partial oxidation of at least one organic compound
US6958414B2 (en) 2002-12-16 2005-10-25 Basf Aktiengesellschaft Preparation of at least one organic compound by heterogeneously catalyzed partial gas-phase oxidation
BRPI0413297B1 (en) 2003-08-06 2014-01-21 PROCESS FOR OPERATING CONTINUOUS PARTIAL OXIDATION IN A GAS-PHASE CATHYGENIZED IN AT LEAST ONE ORGANIC COMPOUND
BRPI0509632B1 (en) 2004-05-07 2015-09-08 Basf Ag process for loading contact tubes from a contact tube bundle in a structured manner
DE102004025445A1 (en) 2004-05-19 2005-02-10 Basf Ag Gas-phase partial oxidation of an organic compound on a heterogeneous catalyst comprises counteracting deactivation of the catalyst by increasing the gas pressure
US7439389B2 (en) 2005-03-01 2008-10-21 Basf Aktiengesellschaft Process for preparing at least one organic target compound by heterogeneously catalyzed gas phase partial oxidation
DE102006000996A1 (en) 2006-01-05 2007-07-12 Basf Ag Heterogeneously catalyzed gas phase partial oxidation of organic compound in fixed catalyst bed involves recovering quality of catalyst bed by replacing its portion, with a catalyst having activity lower than that of the replaced catalyst
EP1734030A1 (en) 2006-01-18 2006-12-20 BASF Aktiengesellschaft Method for long term operation of a heterogeneously catalysed gas phase partial oxidation of an organic educt
DE102007004961A1 (en) 2007-01-26 2008-07-31 Basf Se Preparing a catalyst molded body, useful e.g. to prepare catalyst for gas phase partial oxidation of an organic compound, comprises molding a precursor mixture to a desired geometry, using graphite, and thermally treating the molded body
DE102007017080A1 (en) 2007-04-10 2008-10-16 Basf Se Method for feeding a longitudinal section of a contact tube
DE102007025869A1 (en) 2007-06-01 2008-07-03 Basf Se To service tube bundle of gas-phase hydrocarbon oxidation reactor immediately prior to re-charging with fresh bed of catalyst solids, they are brushed internally
DE102007028332A1 (en) 2007-06-15 2008-12-18 Basf Se A method for feeding a reactor with a fixed catalyst bed comprising at least annular shaped catalyst bodies K.
DE102007028333A1 (en) 2007-06-15 2008-12-18 Basf Se Method for introducing a subset taken from at least one production batch of annular shell catalysts K into a reaction tube of a tube bundle reactor
DE102012212437A1 (en) 2012-07-16 2014-01-16 Basf Se Process for the preparation of acrylic acid from ethylene oxide and carbon monoxide

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GB1170663A (en) * 1967-03-22 1969-11-12 Shell Int Research Process for preparing Silver Catalysts
GB1257352A (en) * 1968-04-24 1971-12-15

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NO130419B (en) 1974-09-02
DD96643A5 (en) 1973-04-05
DE2159346C3 (en) 1982-06-03
CS191201B2 (en) 1979-06-29
DE2159346B2 (en) 1977-09-15
NL7116246A (en) 1972-06-06
CH587080A5 (en) 1977-04-29
JPS5522146B1 (en) 1980-06-14
BE775697A (en) 1972-05-23
IE35857B1 (en) 1976-06-09
AU3631471A (en) 1973-06-07
NL171237C (en) 1983-03-01
IT941880B (en) 1973-03-10
SE374279B (en) 1975-03-03
AU458053B2 (en) 1975-02-20
FR2117183A5 (en) 1972-07-21
SU540554A3 (en) 1976-12-25
IE35857L (en) 1972-06-02
GB1369639A (en) 1974-10-09
DE2159346A1 (en) 1972-06-08
NL171237B (en) 1982-10-01
CA1004214A (en) 1977-01-25

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