CN1401430A - Catalyst for producing ethene by oxidizing ethane with carbon dioxide, and preparing process thereof - Google Patents

Catalyst for producing ethene by oxidizing ethane with carbon dioxide, and preparing process thereof Download PDF

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Publication number
CN1401430A
CN1401430A CN02131334A CN02131334A CN1401430A CN 1401430 A CN1401430 A CN 1401430A CN 02131334 A CN02131334 A CN 02131334A CN 02131334 A CN02131334 A CN 02131334A CN 1401430 A CN1401430 A CN 1401430A
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catalyzer
carbon dioxide
reaction
cobalt
barium carbonate
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CN1132691C (en
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张昕
徐柏庆
叶青
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Tsinghua University
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Tsinghua University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

A catalyst for preparing ethene (C2H4) by oxidizing ethane by CO2 and dehydrogenating C2H6 is prepared through preparing the precursor from aqueous solution of cobalt nitrate and barium carbonate, drying, calcining at 600-750 deg.C, pressing and screening. Its advantages are high selectivity for C2H4 (97.6-6.4%), high C2H4 yield (80.3-6.4%), high mechanical strength and low reaction temp.

Description

The Catalysts and its preparation method that is used for producing ethene by oxidizing ethane with carbon dioxide
Technical field
The present invention relates to a kind of production ethene (C 2H 4) Catalysts and its preparation method, particularly be used for the Catalysts and its preparation method of producing ethene by oxidizing ethane with carbon dioxide.
Be used for carbonic acid gas (CO 2) ethyl oxide (C 2H 6) generation ethene (C 2H 4) Catalysts and its preparation method.
Background technology
C 2H 4It is important basic chemical industry raw material.At present, to C 2H 4Demand increase day by day.C 2H 6With CO 2Prepared in reaction C 2H 4With traditional C 2H 6The high-temperature vapor cracking prepares C 2H 4Process is compared, and has unique advantages, and is low as temperature of reaction, catalyst carbon deposition is few, C 2H 4Selectivity is high.Therefore, carrying out the development of this reaction new catalyst and the exploitation of technological process has great importance.
In recent years, domestic and international investigator is to CO 2Oxidation C 2H 6Become city C 2H 4Catalyzer has carried out significant research.People such as Krylov go up report at " Catal.Today, 1995,24:371 ", with 1.5%K-5.5%Cr-17%Mn/SiO 2During for catalyzer, at 830 ℃, reactant gases air speed 3600h -1, CO in the reactant gases 2/ C 2H 6Under=1.5/1 the condition, obtain C 2H 6Transformation efficiency be 82.6%, CO 2Transformation efficiency be 52.3%, C 2H 4Selectivity be 76.8% result.People such as Wang exist: " Catal.Lett., 1999,629 " go up report, when with 5CrO 3/ 6SO 4 2--SiO 2During for catalyzer, at 650 ℃, reactant gases air speed 3600h -1, CO in the reactant gases 2/ C 2H 6/ N 2Under=1/5/4 the condition, obtain C 2H 6Transformation efficiency be 67.2%, CO 2Transformation efficiency be 21.9%, C 2H 4Selectivity be 81.8% result.People such as Xu go up report at " Catal.Lett., 1999,62:185 ", when being catalyzer with 9Fe-9Mn/Si-2, and at 800 ℃, reactant gases air speed 1000h -1, CO in the reactant gases 2/ C 2H 6Under /=1 the condition, obtain C 2H 6Transformation efficiency be 68.6%, CO 2Transformation efficiency be 39.1%, C 2H 4Selectivity be 92.3% result.
The catalyzer of above bibliographical information respectively has characteristics, but the temperature of reaction during catalyzer performance greater catalytic performance is generally higher, and has CO on the catalyzer of low temperature active 2And C 2H 6Transformation efficiency lower again.
Summary of the invention
The object of the present invention is to provide a kind of Catalysts and its preparation method that is used for producing ethene by oxidizing ethane with carbon dioxide, the catalyzer that is provided can carry out CO under than low reaction temperatures (650～730 ℃) 2Oxidation C 2H 6Dehydrogenation system C 2H 4Reaction, and obtaining higher C 2H 4In the time of selectivity and yield, C 2H 6Transformation efficiency and CO 2Transformation efficiency is also higher; And preparation technology is simple.
The purpose of this invention is to provide that following technical scheme realizes:
A kind of catalyzer that is used for producing ethene by oxidizing ethane with carbon dioxide, this catalyzer are the cobalt/cobalt oxide that barium carbonate supports, and wherein the CoO content range is 1～30wt%, and molecular formula is expressed as Co/BaCO 3
Above-mentioned Preparation of catalysts method provided by the present invention comprises the steps:
(1) cobalt nitrate hexahydrate is dissolved in the deionized water, being made into concentration is 2.6 * 10 -5Mol/mL～7.9 * 10 -4The cobalt nitrate solution of mol/mL;
(2) a certain amount of cobalt nitrate solution is joined barium carbonate (BaCO 3) go in the powder, make the pulpous state precursor;
(3) with the catalyzer precursor 90～120 ℃ of dryings 7～10 hours, then 600～750 ℃ of following roastings 8～12 hours;
(4) compression moulding after the roasting, screening 20～40 orders promptly make described granules of catalyst.
Catalyst performance evaluation is to carry out on high pressure, continuous flow fixed bed reactor.The reaction gas proportioning is CO 2/ C 2H 6/ N 2=10: 10～8: 1, air speed 1800～2400ml/ (g.cat) .h -1, pressure 0.1MPa, temperature of reaction is generally between 650～730 ℃.On such catalyzer, carry out CO 2Oxidation C 2H 6Dehydrogenation prepares C 2H 4Reaction obtains C 2H 4Selectivity is 97.6～6.4%, C 2H 4Yield is 80.3～6.4%, C 2H 6Transformation efficiency is 99.6～29.3%, CO 2Transformation efficiency be 88.6～7.6%.
Catalyzer physical strength provided by the present invention is good, and the preparation method is simple.Because the Co of high oxidation state still can stable existence in reaction in the catalyzer, so catalyzer has than the high CO of most of catalyzer that has reported 2Oxidation C 2H 6Generate C 2H 4Performance, and temperature of reaction is lower.
Embodiment
Used barium carbonate (the BaCO of preparation catalyzer 3) powder is commercially available barium carbonate (BaCO 3) powder, Red Star chemical plant, Beijing produces, analytical pure; Xiao Suangu (Co (NO 3) 26H 2O is that Beijing dicyclo chemical reagent factory produces analytical pure.
The invention will be further described by embodiment below:
Embodiment 1
Is concentration 2.6 * 10 -510mL Xiao Suangu (Co (the NO of mol/mL 3) 26H 2O, Beijing dicyclo chemical reagent factory, analytical pure) aqueous solution joins 2.0g barium carbonate (BaCO 3, Red Star chemical plant, Beijing, analytical pure) go in the powder, 90 ℃ of dryings 10 hours, and made the cobalt/cobalt oxide catalyzer that catalyzer carbonic acid barium supports in 8 hours 750 ℃ of high-temperature roastings, Co content in the catalyzer (calculating with CoO) is 1wt%.Then, catalyzer compression moulding, the screening 20 purpose particles standby.On prepared catalyzer, carry out CO 2Oxidation C 2H 6Generate C 2H 4Reaction.In the reaction gas proportioning is CH 4/ O 2/ N 2=10/10/1, air speed 2000ml/ (g.cat) .h -1, pressure 0.1MPa, temperature of reaction is to carry out under 730 ℃ the condition.Catalyst levels 0.3g.Analytical reaction tail gas, the transformation efficiency that obtains ethane is 96.7%, and carbon dioxide conversion is 83.8%, and ethylene selectivity is 83.0%, and yield of ethene is 80.3%.
Embodiment 2
Is concentration 1.3 * 10 -410mL Xiao Suangu (Co (the NO of mol/mL 3) 26H 2O, Beijing dicyclo chemical reagent factory, analytical pure) aqueous solution joins 2.0g barium carbonate (BaCO 3, Red Star chemical plant, Beijing, analytical pure) go in the powder, 120 ℃ of dryings 7 hours, and made the cobalt/cobalt oxide catalyzer that barium carbonate supports in 9 hours 700 ℃ of high-temperature roastings, Co content in the catalyzer (calculating with CoO) is 5wt%.Then, catalyzer compression moulding, the screening 20 purpose particles standby.On prepared catalyzer, carry out CO 2Oxidation C 2H 6Generate C 2H 4Reaction.In the reaction gas proportioning is CH 4/ O 2/ N 2=10/9/1, air speed 1800ml/ (g.cat) .h -1, pressure 0.1MPa, temperature of reaction is to carry out under 700 ℃ the condition.Catalyst levels 0.3g.Analytical reaction tail gas, the transformation efficiency that obtains ethane is 89.7%, and carbon dioxide conversion is 83.1%, and ethylene selectivity is 66.8%, yield of ethene 60.0%.
Embodiment 3
Is concentration 2.6 * 10 -410mL Xiao Suangu (Co (the NO of mol/mL 3) 26H 2O, Beijing dicyclo chemical reagent factory, analytical pure) aqueous solution joins 2.0g barium carbonate (BaCO 3, Red Star chemical plant, Beijing, analytical pure) go in the powder, 110 ℃ of dryings 8 hours, and made the cobalt/cobalt oxide catalyzer that barium carbonate supports in 10 hours 650 ℃ of high-temperature roastings, Co content in the catalyzer (calculating with CoO) is 10wt%.Then, catalyzer is at 200Kg/cm 2Pressure compression moulding, the screening 30 purpose particles standby.On prepared catalyzer, carry out CO 2Oxidation C 2H 6Generate C 2H 4Reaction.In the reaction gas proportioning is CH 4/ O 2/ N 2=10/10/1, air speed 2200ml/ (g.cat) .h -1, pressure 0.1MPa, temperature of reaction is to carry out under 670 ℃ the condition.Catalyst levels 0.3g.Analytical reaction tail gas, the transformation efficiency that obtains ethane is 83.8%, and carbon dioxide conversion is 74.1%, and ethylene selectivity is 45.8%, and yield of ethene is 38.4%.
Embodiment 4
Is concentration 7.8 * 10 -510mL Xiao Suangu (Co (the NO of mol/mL 3) 26H 2O, Beijing dicyclo chemical reagent factory, analytical pure) aqueous solution joins 2.0g barium carbonate (BaCO 3, Red Star chemical plant, Beijing, analytical pure) go in the powder, 100 ℃ of dryings 9 hours, and made the cobalt/cobalt oxide catalyzer that barium carbonate supports in 12 hours 600 ℃ of high-temperature roastings, Co content in the catalyzer (calculating with CoO) is 3wt%.Then, catalyzer compression moulding, the screening 40 purpose particles standby.On prepared catalyzer, carry out CO 2Oxidation C 2H 6Generate C 2H 4Reaction.In the reaction gas proportioning is CH 4/ O 2/ N 2=10/10/1, air speed 2400ml/ (g.cat) .h -1, pressure 0.1MPa, temperature of reaction is to carry out under 650 ℃ the condition.Catalyst levels 0.3g.Analytical reaction tail gas, the transformation efficiency that obtains ethane is 66.3%, and carbon dioxide conversion is 52.3%, and ethylene selectivity is 93.4%, and yield of ethene is 62.0%.
Embodiment 5
Is concentration 7.8 * 10 -410mL Xiao Suangu (Co (the NO of mol/mL 3) 26H 2O, Beijing dicyclo chemical reagent factory, analytical pure) aqueous solution joins 2.0g barium carbonate (BaCO 3, Red Star chemical plant, Beijing, analytical pure) go in the powder, 100 ℃ of dryings 10 hours, and made the cobalt/cobalt oxide catalyzer that barium carbonate supports in 11 hours 600 ℃ of high-temperature roastings, Co content in the catalyzer (calculating with CoO) is 30wt%.Then, catalyzer compression moulding, the screening 30 purpose particles standby.On prepared catalyzer, carry out CO 2Oxidation C 2H 6Dehydrogenation prepares C 2H 4Reaction.In the reaction gas proportioning is CH 4/ O 2/ N 2=10/10/1, air speed 2400ml/ (g.cat) .h -1, pressure 0.1MPa, temperature of reaction is to carry out under 730 ℃ the condition.Catalyst levels 0.3g.Analytical reaction tail gas, the transformation efficiency that obtains ethane is 94.1%, and carbon dioxide conversion is 88.2%, and ethylene selectivity is 34.7%, and yield of ethene is 32.8%.

Claims (2)

1. catalyzer that is used for producing ethene by oxidizing ethane with carbon dioxide, it is characterized in that: this catalyzer is the cobalt/cobalt oxide that barium carbonate supports, and wherein CoO content is 1～30wt%, and molecular formula is expressed as Co/BaCO 3
2. one kind prepares the method that is used for the catalyzer of producing ethene by oxidizing ethane with carbon dioxide as claimed in claim 1, it is characterized in that this method carries out as follows:
(1) cobalt nitrate hexahydrate is dissolved in the deionized water, being made into concentration is 2.6 * 10 -5Mol/mL～7.9 * 10 -4The cobalt nitrate solution of mol/mL;
(2) a certain amount of cobalt nitrate solution is joined in the barium carbonate powder go, make the precursor of pulpous state;
(3) with the catalyzer precursor 90～120 ℃ of dryings 7～10 hours, then 600～750 ℃ of following roastings 8～12 hours;
(4) compression moulding after the roasting, screening 20～40 orders promptly make described catalyst prod.
CN02131334A 2002-09-29 2002-09-29 Catalyst for producing ethene by oxidizing ethane with carbon dioxide, and preparing process thereof Expired - Fee Related CN1132691C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2025660A3 (en) * 2007-08-14 2009-03-04 Rohm and Haas Company Processes for producing ethylene and carbon monoxide mixtures from ethane

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2025660A3 (en) * 2007-08-14 2009-03-04 Rohm and Haas Company Processes for producing ethylene and carbon monoxide mixtures from ethane
US7906699B2 (en) 2007-08-14 2011-03-15 Rohm And Haas Company Processes for producing ethylene and carbon monoxide mixtures from ethane

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