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CN1318131C - 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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CN1318131C
CN1318131C CNB2004100627086A CN200410062708A CN1318131C CN 1318131 C CN1318131 C CN 1318131C CN B2004100627086 A CNB2004100627086 A CN B2004100627086A CN 200410062708 A CN200410062708 A CN 200410062708A CN 1318131 C CN1318131 C CN 1318131C
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catalyst
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preparation
ethane
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CN1718277A (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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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • 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

本发明涉及一种用于二氧化碳氧化乙烷制乙烯的催化剂及制备方法。本发明针对现有CO2氧化乙烷制乙烯技术中存在的催化剂选择性低的问题，制备出以Cr为主要活性组分、含Ce和Zr、以γ-Al2O3为担体的负载型催化剂，将本催化剂用于CO2氧化乙烷制乙烯的催化反应，乙烷转化率为41.34%～76.71%，乙烯选择性可提高到96.02%～98.84%。The invention relates to a catalyst for oxidizing ethane to ethylene with carbon dioxide and a preparation method. The invention aims at the problem of low catalyst selectivity existing in the existing CO 2 oxidizing ethane to ethylene technology, and prepares a supported catalyst with Cr as the main active component, containing Ce and Zr, and using γ-Al 2 O 3 as the carrier Catalyst, the catalyst is used in the catalytic reaction of CO 2 oxidizing ethane to ethylene, the conversion rate of ethane is 41.34%-76.71%, and the selectivity of ethylene can be increased to 96.02%-98.84%.

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:
C 2H 6+CO 2→C 2H 4+CO+H 2O
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-cat h (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％ Ce0 .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 1Owt％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)

1.一种用于二氧化碳氧化乙烷制乙烯的催化剂，为一种以Cr为主要活性组分，以γ-Al2O3为担体的负载型催化剂，其结构式如下：1. a kind of catalyst that is used for carbon dioxide oxidizing ethane to make ethylene is a kind of with Cr as main active component, with gamma-Al 2 O 3 is the supported catalyst of support, and its structural formula is as follows: Cr/Ce(1-x)ZrxO2/Al2O3式中x＝0.1～0.9Cr/Ce (1-x) Zr x O 2 /Al 2 O 3 where x=0.1～0.9 催化剂各组分的质量百分含量为：Cr为1～15％，Ce(1-x)ZrxO2为2.5～50％，其余为γ-Al2O3。The mass percent content of each component of the catalyst is: 1-15% of Cr, 2.5-50% of Ce (1-x) Zr x O 2 , and the rest of γ-Al 2 O 3 . 2.一种权利要求1催化剂的制备方法，分复合载体制备和催化剂制备两步完成，所用原料的质量比为：Cr(NO3)3·9H2O∶Ce(NO3)3·6H2O∶Zr(NO3)4·5H2O∶γ-Al2O3＝(0.1～12)∶(0.1～8.9)∶(0.1～8.9)∶(3～22)，具体步骤如下：2. A preparation method of the catalyst according to claim 1, which is completed in two steps of composite carrier preparation and catalyst preparation, and the mass ratio of the raw materials used is: Cr(NO 3 ) 3 9H 2 O: Ce(NO 3 ) 3 6H 2 O: Zr(NO 3 ) 4 ·5H 2 O: γ-Al 2 O 3 =(0.1～12):(0.1～8.9):(0.1～8.9):(3～22), the specific steps are as follows: A：复合载体的制备：A: Preparation of composite carrier: 将Ce(NO3)3·6H2O和Zr(NO3)4·5H2O的水溶液混合均匀后，浸渍于粉末状γ-Al2O3担体上，经干燥、焙烧先制成Ce(1-x)ZrxO2/Al2O3复合载体；Mix the aqueous solutions of Ce(NO 3 ) 3 ·6H 2 O and Zr(NO 3 ) 4 ·5H 2 O evenly, impregnate them on the powdery γ-Al 2 O 3 support, dry and roast to make Ce ( 1-x) Zr x O 2 /Al 2 O 3 composite support; B：催化剂的制备：B: Preparation of catalyst: 将Cr(NO3)3·9H2O的水溶液浸渍于步骤A的Ce(1-x)ZrxO2/Al2O3复合载体上，再经干燥、焙烧，制得Cr/Ce(1-x)ZrxO2/Al2O3催化剂。The aqueous solution of Cr(NO 3 ) 3 9H 2 O is impregnated on the Ce (1-x) Zr x O 2 /Al 2 O 3 composite support in step A, then dried and calcined to obtain Cr/Ce (1 -x) Zr x O 2 /Al 2 O 3 catalyst. 3.根据权利要求2的制备方法，其特征是：步骤A中，先将Ce(NO3)3·6H2O和Zr(NO3)4·5H2O的水溶液混合均匀后，浸渍于粉末状γ-Al2O3担体上8～12小时，于90℃～110℃下干燥6～8小时，在500℃焙烧4～6小时，制成Ce(1-x)ZrxO2/Al2O3的复合载体；步骤B中，将Cr(NO3)3·9H2O溶于蒸馏水中，浸渍于步骤A得到的Ce(1-x)ZrxO2/Al2O3复合载体上8～12小时，于90℃～110℃下干燥8～10小时，在400℃焙烧3～4小时，在700℃焙烧5～6小时制得Cr/Ce(1-x)ZrxO2/Al2O3的催化剂。3. The preparation method according to claim 2, characterized in that: in step A, the aqueous solution of Ce(NO 3 ) 3 ·6H 2 O and Zr(NO 3 ) 4 ·5H 2 O is mixed evenly, and then impregnated in the powder γ-Al 2 O 3 support for 8 to 12 hours, dried at 90°C to 110°C for 6 to 8 hours, and calcined at 500°C for 4 to 6 hours to produce Ce (1-x) Zr x O 2 /Al 2 O 3 composite support; in step B, dissolve Cr(NO 3 ) 3 9H 2 O in distilled water, and impregnate the Ce (1-x) Zr x O 2 /Al 2 O 3 composite support obtained in step A Preheat for 8-12 hours, dry at 90°C-110°C for 8-10 hours, bake at 400°C for 3-4 hours, and bake at 700°C for 5-6 hours to obtain Cr/Ce (1-x) Zr x O 2 /Al 2 O 3 catalyst.
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CN1181993A (en) * 1995-08-30 1998-05-20 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
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