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CN1718277A - Catalyst foir preparing ethylene by using ethane as raw material oxidized by carbon dioxide, and its prepn. method - Google Patents

Catalyst foir preparing ethylene by using ethane as raw material oxidized by carbon dioxide, and its prepn. method Download PDF

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CN1718277A
CN1718277A CNA2004100627086A CN200410062708A CN1718277A CN 1718277 A CN1718277 A CN 1718277A CN A2004100627086 A CNA2004100627086 A CN A2004100627086A CN 200410062708 A CN200410062708 A CN 200410062708A CN 1718277 A CN1718277 A CN 1718277A
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roastings
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CN1318131C (en
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季生福
李成岳
陈标华
刘辉
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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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
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

A carried catalyst with high selectivity and conversion rate for preparing ethane from ethane by oxidizing with CO2 is composed of O2 carrier (gamma-Al2O3) and the active component consisting of Cr, Ce and Zr.

Description

A kind of catalyst and preparation method who is used for carbon dioxide ethyl oxide system ethene
Technical field:
The present invention relates to a kind of catalyst and preparation method who is used for carbon dioxide ethyl oxide system ethene.This catalyst is is main active component with Cr, contain Ce and Zr, with γ-Al 2O 3Loaded catalyst for carrier.
Background technology:
Ethene is the basic material of chemical industry.At present, most of ethene is that steam cracking is produced, because the steam cracking power consumption is very big, researches and develops new ethylene production technology and has great importance.Use O 2Though the ethane dehydrogenation system ethene as oxidant is more less than the steam cracking power consumption, O 2Oxidisability stronger, the raising of ethylene selectivity relatively the difficulty.
In recent years, use CO 2Ethyl oxide system ethene has caused great attention both domestic and external.Its reaction equation is as follows:
M.Bhasin etc. " Dehydrogenation and oxydehydrogenation of paraffins toolefins " (Applied Catalysis A:General, 2001, Vol.221 pp.397-419) comments in the literary composition, uses CO 2Ethyl oxide system ethene have reaction temperature low, be difficult for coking, ethylene selectivity height, be difficult for generating C 3Lot of advantages such as hydro carbons and acetylene.In addition, can be in the course of reaction with greenhouse gases CO 2Become useful CO, this is to reducing CO 2Discharging, the protection environment also be very significant.
At present, be used for CO 2In the catalyst of ethyl oxide system ethene, Cr-is catalyst based to be reasonable system.As S.Wang etc. at " Dehydrogenation of ethane with carbon dioxide oversupported chromium oxide catalysts " (Applied Catalysis A:General, 2000, Vol.196 is pp.1-8) with " Effect of promoters on catalytic performance of Cr/SiO 2Catalysts in oxidative dehydrogenation of ethane with carbon dioxide " (CatalysisLetters, 2001, Vol.73 pp.107-111) goes up report, with 8 (wt) %Cr 2O 3/ SiO 2Be catalyst, at 650 ℃, CO 2: C 2H 6Under=5: 1 the condition, the conversion ratio that has obtained ethane is 56.1%, and selectivity of ethylene is 92.9% result.N.Mimura etc. are at " High-performanceCr/H-ZSM-5 catalysts for oxidative dehydrogenation of ethane to ethylene withCO 2As an oxidant " (Catalysis Communications, 2002, Vol.3 pp.257-262) goes up report, Cr/H-ZSM-5 (SiO 2/ Al 2O 3=1900) catalyst is at 923K, CO 2: C 2H 6Under=9: 1 the condition, the conversion ratio that has obtained ethane is 68.2%, and selectivity of ethylene is 69.5% result.
From existing report as can be seen, for CO 2The catalytic reaction of ethyl oxide system ethene has a good ethane conversion though Cr-is catalyst based, and is lower to the directional selectivity of ethene.Simultaneously, because Cr and SiO 2, carrier such as molecular sieve has stronger interaction, active component Cr more easily reunites in the course of reaction, thereby makes activity of such catalysts along with the increase in reaction time descends to some extent.And in the reaction of ethane catalytic cracking ethene, selectivity of ethylene is high more, and the utilization rate of carbon resource is also high more, therefore, improves the directional selectivity of activity of such catalysts, particularly ethene, to CO 2The process of ethyl oxide system ethene has great importance.
Ce (1-x)Zr xO 2Solid solution in supporting the three-effect catalyst for purifying tail gas of car of noble metal, has shown the effect of good dispersion noble metal active component owing to have oxygen storage/releasability and OR performance preferably.But Shang Weijian is used to disperse Cr and preparation Cr/Ce (1-x)Zr xO 2/ Al 2O 3The report of catalyst.
Summary of the invention:
The object of the present invention is to provide a kind of by CO 2As the catalyst and the preparation method of oxidant oxidation ethane system ethene, on the basis of improving catalytic performance, improve directional selectivity to ethene.Utilize this catalyst, ethane and CO 2But the reaction highly selective generates ethene.
The present invention is a kind of catalyst that is used for carbon dioxide ethyl oxide system ethene, is main active component with Cr, with γ-Al 2O 3Be the loaded catalyst of carrier, its structural formula is as follows:
Cr/Ce (1-x)Zr xO 2/ Al 2O 3X=0.1 in the formula～0.9
The quality percentage composition of each component of catalyst is: Cr is 1～15%, Ce (1-x)Zr xO 2(x=0.1～0.9) is 2.5～50%, and all the other are γ-Al 2O 3
The present invention also provides a kind of above-mentioned Preparation of catalysts method, adopts the step impregnation method preparation, divides complex carrier preparation and two steps of Preparation of Catalyst to finish, and raw materials used mass ratio is: Cr (NO 3) 39H 2O: Ce (NO 3) 36H 2O: Zr (NO 3) 45H 2O: γ-Al 2O 3=(0.1～12): (0.1～8.9): (0.1～8.9): (3～22), concrete preparation process is as follows:
A: the preparation of complex carrier:
With Ce (NO 3) 36H 2O and Zr (NO 3) 45H 2After the aqueous solution of O is even, impregnated in Powdered γ-Al 2O 3On the carrier, Ce is made in drying, roasting earlier (1-x)Zr xO 2/ Al 2O 3(x=0.1～0.9) complex carrier;
B: Preparation of catalysts:
With Cr (NO 3) 39H 2The aqueous solution of O impregnated in the Ce of steps A (1-x)Zr xO 2/ Al 2O 3On the complex carrier, drying, roasting make Cr/Ce again (1-x)Zr xO 2/ Al 2O 3(x=0.1～0.9) catalyst.
In above-mentioned preparation process, in the steps A, earlier with Ce (NO 3) 36H 2O and Zr (NO 3) 45H 2After the aqueous solution of O is even, impregnated in Powdered γ-Al 2O 3On the carrier 8～12 hours, under 90 ℃～110 ℃, dry 6～8 hours, under 500 ℃, Ce was made in roasting 4～6 hours (1-x)Zr xO 2/ Al 2O 3The complex carrier of (x=0.1～0.9);
In step B, with Cr (NO 3) 39H 2O is dissolved in the distilled water, impregnated in the Ce that steps A obtains (1-x)Zr xO 2/ Al 2O 3On the complex carrier 8～12 hours, under 90 ℃～110 ℃, dry 8～10 hours, under 400 ℃, roasting 3～4 hours, under 700 ℃, roasting made Cr/Ce in 5～6 hours again (1-x)Zr xO 2/ Al 2O 3The catalyst of (x=0.1～0.9).
In above-mentioned preparation method, to employed Ce (NO 3) 36H 2O and Zr (NO 3) 45H 2The mixed aqueous solution of O and Cr (NO 3) 39H 2The concentration of the aqueous solution of O does not have special requirement, with can submergence γ-Al 2O 3Carrier is as the criterion.
The present invention adopts step impregnation method to prepare catalyst, and what final step was flooded is the active component that contains Cr.Because Cr is immersed in Ce (1-x)Zr xO 2/ Al 2O 3On the complex carrier, thereby can weaken Cr and Al 2O 3Strong interaction, improve the dispersiveness of active component Cr, give full play to the catalytic activity of Cr.Simultaneously, to CO 2Oxidation susceptibility good facilitation is also arranged.
The present invention can obtain the different catalyst of a series of active component contents, and promptly the quality percentage composition scope Cr of catalytic component is 1～15%, Ce (1-x)Zr xO 2(x=0.1～0.9) 2.5～50%, all the other are γ-Al 2O 3Cr/Ce (1-x)Zr xO 2/ Al 2O 3Catalyst.These catalyst can be used for the catalytic reaction of carbon dioxide ethyl oxide system ethene.
Catalyst of the present invention is used for the catalytic reaction of carbon dioxide ethyl oxide system ethene and estimates on the miniature fixed-bed reactor of normal pressure.Its reaction condition is: 500～750 ℃ of reaction temperatures, and reaction pressure 0.1Mpa (MPa), reaction velocity 2400～6000ml/g-cath (milliliter/hour gram catalyst), the unstripped gas of reaction is that mol ratio is 0.125～0.25 C 2H 6/ CO 2Gaseous mixture and carrier gas (N 2).Use catalyst of the present invention to carry out CO 2The catalytic reaction of ethyl oxide system ethene, obtaining ethane conversion is 41.34%～76.71%, ethylene selectivity is 96.02%～98.84%.
By the evaluation of carbon dioxide ethyl oxide system ethylene catalyst reaction, the Cr/Ce of the present invention's preparation (1-x)Zr xO 2/ Al 2O 3Catalyst series has following advantage:
1. under lower reaction temperature, the Cr/Ce of the present invention's preparation (1-x)Zr xO 2/ Al 2O 3Catalyst has high directional selectivity to ethene.
2. Cr is immersed in Ce (1-x)Zr xO 2/ Al 2O 3On the complex carrier, because Ce (1-x)Zr xO 2Solid solution has good oxygen storage/releasability and OR performance, thereby has weakened Cr and Al 2O 3Strong interaction, improved the dispersiveness of active component Cr, given full play to the catalytic activity of Cr, promoted CO 2Oxidation susceptibility.
Below in conjunction with embodiment effect of the present invention is described further.
The specific embodiment:
Embodiment 1
Preparation 1wt%Cr/10wt%Ce 0.5Zr 0.5O 2/ Al 2O 3Catalyst.By preparation method of the present invention, the raw material consumption of preparation 5 gram catalyst is as shown in table 1.Take by weighing the analytically pure Ce (NO of 0.73 gram respectively 3) 36H 2O and the analytically pure Zr (NO of 0.73 gram 3) 45H 2O is dissolved in the 5ml distilled water, impregnated in the γ-Al of 4.45 grams after mixing 2O 3In the powder, room temperature was placed 8 hours, 90 ℃ dry 6 hours down, Ce is made in 500 ℃ of roastings 4 hours 0.5Zr 0.5O 2/ Al 2O 3Complex carrier; Take by weighing the analytically pure Cr (NO of 0.38 gram then 3) 39H 2O is dissolved in the distilled water of 5ml, impregnated in Ce 0.5Zr 0.5O 2/ Al 2O 3In the complex carrier, room temperature was placed 12 hours, and 110 ℃ were descended dry 10 hours, and 400 ℃ of roastings 4 hours, made 1wt%Cr/10wt%Ce in 6 hours 700 ℃ of roastings again 0.5Zr 0.5O 2/ Al 2O 3Catalyst.
Catalyst is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction is listed in the table 2.
Embodiment 2
Preparation 2wt%Cr/10wt%Ce 0.5Zr 0.5O 2/ Al 2O 3Catalyst.By preparation method of the present invention, the raw material consumption of preparation 5 gram catalyst is as shown in table 1.Take by weighing the analytically pure Ce (NO of 0.73 gram respectively 3) 36H 2O and the analytically pure Zr (NO of 0.73 gram 3) 45H 2O is dissolved in the 5ml distilled water, impregnated in the γ-Al of 4.40 grams after mixing 2O 3In the powder, room temperature was placed 12 hours, 110 ℃ dry 8 hours down, Ce is made in 500 ℃ of roastings 6 hours 0.5Zr 0.5O 2/ Al 2O 3Complex carrier; Take by weighing the analytically pure Cr (NO of 0.77 gram then 3) 39H 2O is dissolved in the distilled water of 5ml, impregnated in Ce 0.5Zr 0.5O 2/ Al 2O 3In the complex carrier, room temperature was placed 8 hours, and 90 ℃ were descended dry 8 hours, and 400 ℃ of roastings 3 hours, made 2wt%Cr/10wt%Ce in 5 hours 700 ℃ of roastings 0.5Zr 0.5O 2/ Al 2O 3Catalyst.Catalyst is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction is listed in the table 2.
Embodiment 3
Preparation 4wt%Cr/10wt%Ce 0.5Zr 0.5O 2/ Al 2O 3Catalyst.By preparation method of the present invention, the raw material consumption of preparation 5 gram catalyst is as shown in table 1.Take by weighing the analytically pure Ce (NO of 0.73 gram respectively 3) 36H 2O and the analytically pure Zr (NO of 0.73 gram 3) 45H 2O is dissolved in the 5ml distilled water, impregnated in the γ-Al of 4.30 grams after mixing 2O 3In the powder, room temperature was placed 10 hours, 100 ℃ dry 7 hours down, Ce is made in 500 ℃ of roastings 5 hours 0.5Zr 0.5O 2/ Al 2O 3Complex carrier; Take by weighing the analytically pure Cr (NO of 1.54 grams then 3) 39H 2O is dissolved in the distilled water of 5ml, impregnated in Ce 0.5Zr 0.5O 2/ Al 2O 3In the complex carrier, room temperature was placed 11 hours, and 100 ℃ were descended dry 10 hours, and 400 ℃ of roastings 4 hours, made 4wt%Cr/10wt%Ce in 5 hours 700 ℃ of roastings 0.5Zr 0.5O 2/ Al 2O 3Catalyst.Catalyst is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction is listed in the table 2.
Embodiment 4
Preparation 6wt%Cr/10wt%Ce 0.5Zr 0.5O 2/ Al 2O 3Catalyst.By preparation method of the present invention, the raw material consumption of preparation 5 gram catalyst is as shown in table 1.Take by weighing the analytically pure Ce (NO of 0.73 gram respectively 3) 36H 2O and the analytically pure Zr (NO of 0.73 gram 3) 45H 2O is dissolved in the 5ml distilled water, impregnated in 4.20 gram γ-Al after mixing 2O 3In the powder, room temperature was placed 12 hours, 90 ℃ dry 6 hours down, Ce is made in 500 ℃ of roastings 5 hours 0.5Zr 0.5O 2/ Al 2O 3Complex carrier; Take by weighing the analytically pure Cr (NO of 2.31 grams then 3) 39H 2O is dissolved in the distilled water of 5ml, impregnated in Ce 0.5Zr 0.5O 2/ Al 2O 3In the complex carrier, room temperature was placed 12 hours, and 110 ℃ were descended dry 5 hours, and 400 ℃ of roastings 3 hours, made 6wt%Cr/10wt%Ce in 5 hours 700 ℃ of roastings 0.5Zr 0.5O 2/ Al 2O 3Catalyst.Catalyst is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction is listed in the table 2.
Embodiment 5
Preparation 10wt%Cr/10wt%Ce 0.5Zr 0.5O 2/ Al 2O 3Catalyst.By preparation method of the present invention, the raw material consumption of preparation 5 gram catalyst is as shown in table 1.Take by weighing the analytically pure Ce (NO of 0.73 gram respectively 3) 36H 2O and the analytically pure Zr (NO of 0.73 gram 3) 45H 2O is dissolved in the 5ml distilled water, impregnated in 4.00 gram γ-Al after mixing 2O 3In the powder, room temperature was placed 12 hours, 90 ℃ dry 5 hours down, Ce is made in 500 ℃ of roastings 4 hours 0.5Zr 0.5O 2/ Al 2O 3Complex carrier; Take by weighing the analytically pure Cr (NO of 3.85 grams then 3) 39H 2O is dissolved in the distilled water of 6ml, impregnated in Ce 0.5Zr 0.5O 2/ Al 2O 3In the complex carrier, room temperature was placed 11 hours, and 110 ℃ were descended dry 10 hours, and 400 ℃ of roastings 4 hours, made 10wt%Cr/10wt%Ce in 5 hours 700 ℃ of roastings 0.5Zr 0.5O 2/ Al 2O 3Catalyst.Catalyst is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction is listed in the table 2.
Embodiment 6
Preparation 15wt%Cr/10wt%Ce 0.5Zr 0.5O 2/ Al 2O 3Catalyst.By preparation method of the present invention, the raw material consumption of preparation 5 gram catalyst is as shown in table 1.Take by weighing the analytically pure Ce (NO of 0.73 gram respectively 3) 36H 2O and the analytically pure Zr (NO of 0.73 gram 3) 45H 2O is dissolved in the 4ml distilled water, impregnated in 3.75 gram γ-Al after mixing 2O 3In the powder, room temperature was placed 10 hours, 110 ℃ dry 5 hours down, Ce is made in 500 ℃ of roastings 4 hours 0.5Zr 0.5O 2/ Al 2O 3Complex carrier; Take by weighing the analytically pure Cr (NO of 5.77 grams then 3) 39H 2O is dissolved in the distilled water of 6ml, impregnated in Ce 0.5Zr 0.5O 2/ Al 2O 3In the complex carrier, room temperature was placed 10 hours, and 110 ℃ were descended dry 8 hours, and 400 ℃ of roastings 3 hours, made 15wt%Cr/10wt%Ce in 6 hours 700 ℃ of roastings 0.5Zr 0.5O 2/ Al 2O 3Catalyst.Catalyst is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction is listed in the table 2.
Embodiment 7
Preparation 6wt%Cr/2.5wt%Ce 0.9Zr 0.1O 2/ Al 2O 3Catalyst.By preparation method of the present invention, the raw material consumption of preparation 5 gram catalyst is as shown in table 1.Take by weighing the analytically pure Ce (NO of 0.29 gram respectively 3) 36H 2O and the analytically pure Zr (NO of 0.03 gram 3) 45H 2O is dissolved in the 5ml distilled water, impregnated in 4.58 gram γ-Al after mixing 2O 3In the powder, room temperature was placed 12 hours, 110 ℃ dry 5 hours down, Ce is made in 500 ℃ of roastings 4 hours 0.9Zr 0.1O 2/ Al 2O 3Complex carrier; Take by weighing the analytically pure Cr (NO of 2.31 grams then 3) 39H 2O is dissolved in the distilled water of 5ml, impregnated in Ce 0.9Zr 0.1O 2/ Al 2O 3In the complex carrier, room temperature was placed 11 hours, and 110 ℃ were descended dry 8 hours, and 400 ℃ of roastings 4 hours, made 6wt%Cr/2.5wt%Ce in 5 hours 700 ℃ of roastings 0.9Zr 0.1O 2/ Al 2O 3Catalyst.Catalyst is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction is listed in the table 2.
Embodiment 8
Preparation 6wt%Cr/5wt%Ce 0.7Zr 0.3O 2/ Al 2O 3Catalyst.By preparation method of the present invention, the raw material consumption of preparation 5 gram catalyst is as shown in table 1.Take by weighing the analytically pure Ce (NO of 0.48 gram respectively 3) 36H 2O and the analytically pure Zr (NO of 0.20 gram 3) 45H 2O is dissolved in the 5ml distilled water, impregnated in 4.45 gram γ-Al after mixing 2O 3In the powder, room temperature was placed 11 hours, 90 ℃ dry 8 hours down, Ce is made in 500 ℃ of roastings 5 hours 0.7Zr 0.3O 2/ Al 2O 3Complex carrier; Take by weighing the analytically pure Cr (NO of 2.31 grams then 3) 39H 2O is dissolved in the distilled water of 5ml, impregnated in Ce 0.7Zr 0.3O 2/ Al 2O 3In the complex carrier, room temperature was placed 12 hours, did 8 hours down, 400 ℃ of roastings 3 hours, made 6wt%Cr/5wt%Ce in 5 hours 700 ℃ of roastings for 110 ℃ 0.7Zr 0.3O 2/ Al 2O 3Catalyst.Catalyst is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction is listed in the table 2.
Embodiment 9
Preparation 6wt%Cr/25wt%Ce 0.3Zr 0.7O 2/ Al 2O 3Catalyst.By preparation method of the present invention, the raw material consumption of preparation 5 gram catalyst is as shown in table 1.Take by weighing the analytically pure Ce (NO of 1.18 grams respectively 3) 36H 2O and the analytically pure Zr (NO of 2.72 grams 3) 45H 2O is dissolved in the 6ml distilled water, impregnated in 3.45 gram γ-Al after mixing 2O 3In the powder, room temperature was placed 10 hours, 110 ℃ dry 6 hours down, Ce is made in 500 ℃ of roastings 4 hours 0.3Zr 0.7O 2/ Al 2O 3Complex carrier; Take by weighing the analytically pure Cr (NO of 2.31 grams then 3) 39H 2O is dissolved in the distilled water of 5ml, impregnated in Ce 0.3Zr 0.7O 2/ Al 2O 3In the complex carrier, room temperature was placed 12 hours, and 90 ℃ were descended dry 12 hours, and 400 ℃ of roastings 4 hours, made 6wt%Cr/25wt%Ce in 5 hours 700 ℃ of roastings 0.3Zr 0.7O 2/ Al 2O 3Catalyst.Catalyst is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction is listed in the table 2.
Embodiment 10
Preparation 6wt%Cr/50wt%Ce 0.1Zr 0.9O 2/ Al 2O 3Catalyst.By preparation method of the present invention, the raw material consumption of preparation 5 gram catalyst is as shown in table 1.Take by weighing the analytically pure Ce (NO of 0.85 gram respectively 3) 36H 2O and the analytically pure Zr (NO of 7.54 grams 3) 45H 2O is dissolved in the 8ml distilled water, impregnated in 2.20 gram γ-Al after mixing 2O 3In the powder, room temperature was placed 12 hours, 90 ℃ dry 6 hours down, Ce is made in 500 ℃ of roastings 4 hours 0.1Zr 0.9O 2/ Al 2O 3Complex carrier; Take by weighing the analytically pure Cr (NO of 2.31 grams then 3) 39H 2O is dissolved in the distilled water of 4ml, impregnated in Ce 0.1Zr 0.9O 2/ Al 2O 3In the complex carrier, room temperature was placed 12 hours, and 110 ℃ were descended dry 10 hours, and 400 ℃ of roastings 4 hours, made 6wt%Cr/50wt%Ce in 5 hours 700 ℃ of roastings 0.1Zr 0.9O 2/ Al 2O 3Catalyst.Catalyst is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction is listed in the table 2.
Table 1 is Cr/Ce of the present invention (1-x)Zr xO 2/ Al 2O 3The raw material consumption of (x=0.1～0.9) catalyst series.
Table 2 is that the catalyst of embodiment 1～10 is used for CO 2The evaluation result of ethyl oxide system ethylene catalyst reaction.As can be seen from Table 2, Cr/Ce of the present invention (1-x)Zr xO 2/ Al 2O 3(x=0.1～0.9) catalyst series has fabulous ethene directional selectivity when guaranteeing to have certain ethane conversion.
Table 1
Embodiment Metal nitrate The quality of nitrate (g) Al 2O 3Quality (g) Catalyst is formed
1 Cr(NO 3) 3·9H 2O 0.38 4.45 1wt％Cr/10wt％Ce 0.5Zr 0.5O 2/Al 2O 3
Ce(NO 3) 3·6H 2O 0.73
Zr(NO 3) 4·5H 2O 0.73
2 Cr(NO 3) 3·9H 2O 0.77 4.40 2wt％Cr/10wt％Ce 0.5Zr 0.5O 2/Al 2O 3
Ce(NO 3) 3·6H 2O 0.73
Zr(NO 3) 4·5H 2O 0.73
3 Cr(NO 3) 3·9H 2O 1.54 4.30 4wt％Cr/10wt％Ce 0.5Zr 0.5O 2/Al 2O 3
Ce(NO 3) 3·6H 2O 0.73
Zr(NO 3) 4·5H 2O 0.73
4 Cr(NO 3) 3·9H 2O 2.31 4.20 6wt％Cr/10wt％Ce 0.5Zr 0.5O 2/Al 2O 3
Ce(NO 3) 3·6H 2O 0.73
Zr(NO 3) 4·5H 2O 0.73
5 Cr(NO 3) 3·9H 2O 3.85 4.00 10wt％Cr/10wt％Ce 0.5Zr 0.5O 2/Al 2O 3
Ce(NO 3) 3·6H 2O 0.73
Zr(NO 3) 4·5H 2O 0.73
6 Cr(NO 3) 3·9H 2O 5.77 3.75 15wt％Cr/10wt％Ce 0.5Zr 0.5O 2/Al 2O 3
Ce(NO 3) 3·6H 2O 0.73
Zr(NO 3) 4·5H 2O 0.73
7 Cr(NO 3) 3·9H 2O 2.31 4.58 6wt％Cr/2.5wt％Ce 0.9Zr 0.1O 2/Al 2O 3
Ce(NO 3) 3·6H 2O 0.29
Zr(NO 3) 4·5H 2O 0.03
8 Cr(NO 3) 3·9H 2O 2.31 4.45 6wt％Cr/5wt％Ce 0.7Zr 0.3O 2/Al 2O 3
Ce(NO 3) 3·6H 2O 0.48
Zr(NO 3) 4·5H 2O 0.20
9 Cr(NO 3) 3·9H 2O 2.31 3.45 6wt％Cr/25wt％Ce 0.3Zr 0.7O 3/Al 2O 3
Ce(NO 3) 3·6H 2O 1.18
Zr(NO 3) 4·5H 2O 2.72
10 Cr(NO 3) 3·9H 2O 2.31 2.20 6wt％Cr/50wt％Ce 0.1Zr 0.9O 2/Al 2O 3
Ce(NO 3) 3·6H 2O 0.85
Zr(NO 3) 4·5H 2O 7.54
Table 2
Embodiment Catalyst is formed Reaction temperature (℃) Ethane/CO 2(mol ratio) Reaction velocity (ml/g-cat h) The conversion ratio of ethane (mol%) Selectivity of ethylene (mol%) The yield of ethene (mol%)
1 1wt％Cr/10wt％ Ce 0.5Zr 0.5O 2/Al 2O 3 700 0.25 6000 41.34 96.94 40.05
2 2wt％Cr/10wt％ Ce 0.5Zr 0.5O 2/Al 2O 3 700 0.25 6000 43.09 96.98 41.79
3 4wt％Cr/10wt％ Ce 0.5Zr 0.5O 2/Al 2O 3 700 0.25 6000 49.48 96.62 47.81
4 6wt％Cr/10wt％ Ce 0.5Zr 0.5O 2/Al 2O 3 700 0.25 6000 56.72 98.84 56.06
5 10wt％Cr/10wt％ Ce 0.5Zr 0.5O 2/Al 2O 3 700 0.25 6000 51.35 96.42 49.51
6 15wt％Cr/10wt％ Ce 0.5Zr 0.5O 2/Al 2O 3 700 0.25 6000 50.21 96.35 48.38
7 6wt％Cr/2.5wt％ Ce 0.9Zr 0.1O 2/Al 2O 3 650 0.125 4000 48.16 96.21 46.33
8 6wt％Cr/5wt％ Ce 0.7Zr 0.3O 2/Al 2O 3 680 0.125 4000 51.63 96.34 49.74
9 6wt％Cr/25wt％ Ce 0.3Zr 0.7O 2/Al 2O 3 720 0.167 2500 69.68 96.64 67.34
10 6wt％Cr/50wt％ Ce 0.1Zr 0.9O 2/Al 2O 3 750 0.167 2500 76.71 96.02 73.66

Claims (3)

1. catalyst that is used for carbon dioxide ethyl oxide system ethene, for a kind of be main active component with Cr, with γ-Al 2O 3Be the loaded catalyst of carrier, its structural formula is as follows:
Cr/Ce (1-x)Zr xO 2/ Al 2O 3X=0.1 in the formula～0.9
The quality percentage composition of each component of catalyst is: Cr is 1～15%, Ce (1-x)Zr xO 2(x=0.1～0.9) is 2.5～50%, and all the other are γ-Al 2O 3
2. claim 1 a Preparation of catalysts method divides complex carrier preparation and two steps of Preparation of Catalyst to finish, and raw materials used mass ratio is: Cr (NO 3) 39H 2O: Ce (NO 3) 36H 2O: Zr (NO 3) 45H 2O: γ-Al 2O 3=(0.1～12): (0.1～8.9): (0.1～8.9): (3～22), concrete steps are as follows:
A: the preparation of complex carrier:
With Ce (NO 3) 36H 2O and Zr (NO 3) 45H 2After the aqueous solution of O is even, impregnated in Powdered γ-Al 2O 3On the carrier, Ce is made in drying, roasting earlier (1-x)Zr xO 2/ Al 2O 3Complex carrier;
B: Preparation of catalysts:
With Cr (NO 3) 39H 2The aqueous solution of O impregnated in the Ce of steps A (1-x)Zr xO 2/ Al 2O 3On the complex carrier, drying, roasting make Cr/Ce again (1-x)Zr xO 2/ Al 2O 3(x=0.1～0.9) catalyst.
3. according to the preparation method of claim 2, it is characterized in that: in the steps A, earlier with Ce (NO 3) 36H 2O and Zr (NO 3) 45H 2After the aqueous solution of O is even, impregnated in Powdered γ-Al 2O 3On the carrier 8～12 hours, in 90 ℃～110 ℃ dry 6～8 hours down, 500 ℃ of roastings 4～6 hours, make Ce (1-x)Zr xO 2/ Al 2O 3The complex carrier of (x=0.1～0.9); Among the step B, with Cr (NO 3) 39H 2O is dissolved in the distilled water, impregnated in the Ce that steps A obtains (1-x)Zr xO 2/ Al 2O 3On the complex carrier 8～12 hours, in 90 ℃～110 ℃ dry 8～10 hours down, 400 ℃ of roastings 3～4 hours, made Cr/Ce in 5～6 hours 700 ℃ of roastings (1-x)Zr xO 2/ Al 2O 3The catalyst of (x=0.1～0.9).
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Cited By (2)

* Cited by examiner, † Cited by third party
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EP2025660A3 (en) * 2007-08-14 2009-03-04 Rohm and Haas Company Processes for producing ethylene and carbon monoxide mixtures from ethane
US10662127B2 (en) 2017-08-28 2020-05-26 8 Rivers Capital, Llc Oxidative dehydrogenation of ethane using carbon dioxide

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* Cited by examiner, † Cited by third party
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CN1087654C (en) * 1995-08-30 2002-07-17 中国科学院大连化学物理研究所 Reaction process for preparing low-carbon olefine from low-carbon alkane and catalyst thereof
JP3790142B2 (en) * 2001-09-05 2006-06-28 独立行政法人科学技術振興機構 Catalyst for producing carbon monoxide and ethylene from carbon dioxide and ethane and preparation method thereof

Cited By (4)

* 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
US10662127B2 (en) 2017-08-28 2020-05-26 8 Rivers Capital, Llc Oxidative dehydrogenation of ethane using carbon dioxide
US11174208B2 (en) 2017-08-28 2021-11-16 8 Rivers Capital, Llc Oxidative dehydrogenation of ethane using carbon dioxide

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