CN105013484A - Carbon-alumina supported copper oxide catalyst, preparation method and applications thereof - Google Patents
Carbon-alumina supported copper oxide catalyst, preparation method and applications thereof Download PDFInfo
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- CN105013484A CN105013484A CN201410151212.XA CN201410151212A CN105013484A CN 105013484 A CN105013484 A CN 105013484A CN 201410151212 A CN201410151212 A CN 201410151212A CN 105013484 A CN105013484 A CN 105013484A
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- carbon
- alumina
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- oxide catalyst
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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
Abstract
The present invention discloses a carbon-alumina supported copper oxide catalyst and a preparation method thereof, and applications of the carbon-alumina supported copper oxide catalyst in isobutene preparation through isobutane dehydrogenation, wherein the carbon-alumina supported copper oxide catalyst comprises 4.0-25.0% by mass of an active component copper oxide and the balance of a carbon-alumina composite carrier. According to the present invention, the carbon-alumina supported copper oxide catalyst has characteristics of high isobutane conversion rate, high isobutene selectivity and good stability, wherein the isobutane conversion rate can achieve 35.2-55.4%, the isobutene selectivity can achieve 80.4-92.5%, and the catalyst activity is reduced by 1.5-6.5% after the reaction for 3-5 h; and the catalyst does not use the precious metal and the toxic chromium-based metal oxide, and the method has characteristics of low cost, environmental protection and simple preparation, and is suitable for industrial production.
Description
Technical field
The present invention relates to dehydrogenation loaded catalyst, particularly a kind of carbon-alumina load copper oxide catalyst and preparation method thereof, and it prepares the application in isobutene at dehydrogenation of isobutane.
Background technology
Isobutene is a kind of important Organic Chemicals, not only may be used for synthesizing butyl rubber, isoprene rubber and Oppanol elastomer, also can be used for producing the multiple fine chemicals such as methyl methacrylate, tert-butyl group alcohol simultaneously.The traditional source of isobutene mainly comes from naphtha pyrolysis ethylene unit and refinery fluid catalytic cracking unit, along with continually developing of isobutene downstream product and derivative thereof, the demand of isobutene also increases day by day, and traditional source has been difficult to meet its market demand.For this reason, now constantly seek both at home and abroad and be proposed novel isobutene production technology successively, wherein dehydrogenation of isobutane is one of technology of most competitiveness.China's iso-butane aboundresources, except 4,000,000 tons of catalytic cracking unit annual output, iso-butane is also extensively present in natural gas and other C 4 fractions.Current, domestic iso-butane is mainly as civil LPG fuel, and value is lower.Therefore, the catalyst developing dehydrogenation of isobutane production high added value isobutene has significant economic and social benefit.
Preparing isobutene through dehydrogenation of iso-butane has anaerobic dehydrogenation and aerobic dehydrogenation two kinds of reaction paths.Anaerobic dehydrogenation can obtain higher iso-butane conversion ratio and selective isobutene, now industrialized preparing isobutene through dehydrogenation of iso-butane technique all adopts this route, comprises the Linde technique of the Catofin technique of ABB Lummus company, the FBD-4 technique of Snamprogetti company, the Oleflex technique of Uop Inc., the STAR technique of Philips company and Linde company.Anaerobic dehydrogenation adopts Cr usually
2o
3series catalysts or precious metals pt series catalysts.With Cr
2o
3for the catalyst of representative has high toxicity, do not meet environmental requirement and the shortcoming such as inactivation is fast; So that the catalyst that the noble metals such as Pt system are representative is expensive, inactivation is fast.
Compared with anaerobic dehydrogenation, although the dehydrogenation of iso-butane aerobic significantly can reduce reaction temperature, during using oxygen as oxidant, there is deep oxidation and the product distribution problem such as restive in reaction, this has been reported in many documents.As: Grabowski etc. by cupric oxide load at SiO
2, Al
2o
3, TiO
2, ZrO
2with on the different carriers such as MgO, research finds the CrOx/TiO that K modifies
2with the CrOx/Al that K modifies
2o
3can obtain the highest isobutene yield, be 9.6% and 9%(Applied Catalysis A:General, 144 volume 335-341 pages in 1996).Ni is incorporated into Al by the people such as Vislovskiy
2o
3in the V-Sb-O catalyst of load, iso-butane conversion ratio can be made to be increased to 42-44% by 36%, selective isobutene close to 70%(Applied Catalysis A:General, 250 volumes the 143rd – 150 pages in 2003).The people such as Kaddouri find that iso-butane is at NiMoO
4/ 0.25%K catalyst can be converted into isobutene, but conversion ratio and isobutene yield all lower (AppliedCatalysis A:General, 169 volume L3-L7 pages in 1998).
There is the research report substituting dioxygen oxidation preparing isobutene through dehydrogenation of iso-butane with carbon dioxide in recent years.Dehydrogenation and water-gas reverse shift reaction are coupled by this reaction, promote that iso-butane is to the further conversion in isobutene direction, thus improve iso-butane conversion ratio and selective isobutene; Meanwhile, carbon dioxide reduces the degree of oxidation of isobutene for oxo-dehydrogenation reaction as a kind of oxidant of gentleness, avoids deep oxidation.Catalyst mainly contains V-Mg-O metal oxide (CatalysisCommunications, 11 volumes the 132nd – 136 pages in 2009) and activated carbon loaded cupric oxide, iron oxide and nickel oxide system (US20040181107; Chinese Chemical Letters, 19 volumes the 1059th – 1062 pages in 2008; Applied Catalysis A:General, 168 volume 243-250 pages in 1998; Journal of Molecular Catalysis A:Chemical, 315 volumes the 221st – 225 pages in 2010).But these catalyst in iso-butane carbon dioxide oxidative dehydrogenation process, all there is active lifetime limited, be difficult to the defects such as industrial application.
Carrier made by industrialized catalyst for preparing isobutene through dehydrogenation of iso-butane many employings aluminium oxide.Aluminium oxide has excellent performance in intensity, pore structure and specific area etc., and alumina carrier surface has certain acidity, and this is conducive to the dehydrogenation reaction of iso-butane.But alumina carrier surface has certain hydrophily, and easy carbon distribution, cause catalyst activity reduction.Carbon carrier character is different from aluminium oxide, and such as carbon has good thermal conductivity, and surface has certain hydrophobicity, and carrier surface not easily carbon distribution.These character are conducive to the stability strengthening dehydrogenation of isobutane catalyst.
The present invention is intended to from raising catalytic mechanical intensity, reduces carbon distribution angle, with the cupric oxide of carbon-alumina composite carrier load cheapness, for carbon dioxide oxidation dehydrogenation of isobutane.
Summary of the invention
An object of the present invention is to provide a kind of carbon-alumina load copper oxide catalyst for dehydrogenation of isobutane reaction, utilizes the advantage of carbon and alumina support, obtains better catalytic dehydrogenation performance.
Two of object is the preparation method providing this catalyst.
Three of object is to provide this catalyst to prepare application in isobutene at dehydrogenation of isobutane.
In order to realize foregoing invention object, the present invention is by the following technical solutions: a kind of carbon-alumina load copper oxide catalyst, the carrier that described catalyst comprises and active component, described carrier is carbon-alumina composite carrier, described active component is cupric oxide, and content is 4.0% ~ 25.0% of gross mass.
Described carbon-alumina composite carrier is porous material, and wherein the content of carbon in complex carrier is 5.0% ~ 25.0% of complex carrier quality.
A preparation method for carbon-alumina load copper oxide catalyst, comprises the following steps:
(1) by copper-containing compound and citric acid according to the mass ratio of copper simple substance and citric acid be the ratio mixing of 1:1.6 ~ 1:4.9, being dissolved in water and being made into copper simple substance mass concentration is the solution of 1.59 ~ 2.39g/L.
(2) in the solution prepared in step 1, add carbon-alumina composite carrier, additional proportion is 3.76 ~ 30.04g/g copper simple substance, stirs, dries, roasting, obtains carbon-alumina load copper oxide catalyst.
Described copper-containing compound is copper nitrate, copper sulphate, Schweinfurt green or copper chloride.
In the roasting process of step 2, adopt inert atmosphere, described inert atmosphere is for referring to O
2volumetric concentration lower than 0.1% high-purity N
2, high-purity Ar or high-purity He gas.
Described carbon-alumina composite carrier adopts hydro carbons, carbohydrate, be carbon source containing carbon polymer or pitch, with vapour deposition or liquid impregnation and the process of carbonization carries out the surface-carbon-modified cathode of aluminium oxide.
Carbon-alumina load copper oxide catalyst prepares the application in isobutene at dehydrogenation of isobutane, by described carbon-alumina load copper oxide catalyst filling in the reactor, control temperature of reactor at 540 ~ 620 DEG C, pressure 0.1 ~ 0.5MPa, pass into be preheated to 330 ~ 420 DEG C, the ratio of amount of substance is iso-butane and the carbon dioxide mix gas of 1:5 ~ 1:12, air speed is 0.5 ~ 8L/ (g
cath).
Described reactor is fixed bed reactors, fluidized-bed reactor or moving-burden bed reactor.
The present invention is intended to from raising catalytic mechanical intensity, reduces carbon distribution angle, with the cupric oxide of carbon-alumina composite carrier load cheapness, the carbon provided-alumina load copper oxide catalyst can not only obtain higher iso-butane conversion ratio and selective isobutene, and catalyst stability is better.The conversion ratio of iso-butane can reach 35.2% ~ 55.4%, and selective isobutene can reach 80.4% ~ 92.5%, and reaction 3 ~ 5h rear catalyst activity decrease 1.5% ~ 6.5%, has good industrial applications prospect.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
By Woelm Alumina, (specific area is about 210m
2/ g) flood sucrose solution (sucrose: alumina weight is 0.9:1), then after 120 DEG C of dry 12h, under 800 DEG C of nitrogen protections, roasting carbonization 1h, obtains C-Al
2o
3complex carrier, the content of carbon is 5.0wt%.2.42g copper nitrate and 1.02g citric acid are dissolved in 400mL water, under stirring at room temperature, become solution, in above-mentioned solution, add prepared C-Al
2o
3complex carrier 19.12g, stirring and drying in 60 DEG C of waters bath with thermostatic control, roasting 5h at 650 DEG C, obtains carbon-alumina load copper oxide catalyst CuO/C-Al
2o
3, wherein CuO mass percentage is 4.0%.By prepared CuO/C-Al
2o
3catalyst loads in fixed bed reactors, and passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 330 DEG C is 1:5, is 4L/ (g in 0.1MPa, air speed
cath) with under the condition of reaction temperature 540 DEG C, the conversion ratio recording iso-butane is 35.2%, and selective isobutene is 92.5%, and after reaction 3h, the conversion ratio of iso-butane drops to 33.7%.
Embodiment 2
By Woelm Alumina, (specific area is about 200m
2/ g) pass into C
6h
6/ N
2(25 DEG C of saturated vapors) air-flow, at 725 DEG C, vapour deposition 1h, obtains C-Al
2o
3complex carrier, the content of carbon is 15.2wt%.1.82g Schweinfurt green and 2.10g citric acid are dissolved in 350mL water, under stirring at room temperature, become solution, in above-mentioned solution, add prepared C-Al
2o
3complex carrier 7.17g, stirring and drying in 70 DEG C of waters bath with thermostatic control, roasting 5h at 650 DEG C, obtains carbon-alumina load copper oxide catalyst CuO/C-Al
2o
3, wherein CuO mass percentage is 10.0%.By prepared CuO/C-Al
2o
3catalyst loads in fixed bed reactors, and passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 330 DEG C is 1:5, is 6L/ (g in 0.1MPa, air speed
cath) with under the condition of reaction temperature 555 DEG C, the conversion ratio recording iso-butane is 43.9%, and selective isobutene is 90.4%, and after reaction 4h, the conversion ratio of iso-butane drops to 40.7%.
Embodiment 3
By Woelm Alumina, (specific area is about 200m
2/ g) room temperature volumetric dipping furfuryl alcohol, ethanolic solution (0.5mL furfuryl alcohol: 1g Al
2o
3), then at 95 DEG C, carry out polymerisation, under nitrogen protection, in 800 DEG C of roasting carbonization 1h, obtain C-Al
2o
3complex carrier, the content of carbon is 20.1wt%.2.66g copper sulphate and 3.72g citric acid are dissolved in 450mL water, stirring at room temperature becomes solution, in above-mentioned solution, add prepared C-Al
2o
3complex carrier 6.51g, dries in 80 DEG C of waters bath with thermostatic control, 600 DEG C of roasting 7h, obtains carbon-alumina load copper oxide catalyst CuO/C-Al
2o
3, wherein CuO mass percentage is 15.5%.By prepared CuO/C-Al
2o
3catalyst loads in fixed bed reactors, and passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 420 DEG C is 1:6, is 5L/ (g in 0.2MPa, air speed
cath) with under the condition of reaction temperature 580 DEG C, the conversion ratio recording iso-butane is 47.1%, and selective isobutene is 88.7%, and after reaction 5h, the conversion ratio of iso-butane drops to 42.1%.
Embodiment 4
By Woelm Alumina, (specific area is about 200m
2/ g) impregnating pitch/acetone soln (pitch: alumina weight is 1.0:1), then after 120 DEG C of dry 12h, under 800 DEG C of nitrogen protections, roasting carbonization 1h, obtains C-Al
2o
3complex carrier, the content of carbon is 25.0wt%.2.56g copper chloride and 4.68g citric acid are dissolved in 400mL water, under stirring at room temperature, become solution, in above-mentioned solution, add prepared C-Al
2o
3complex carrier 4.60g, stirring and drying in 90 DEG C of waters bath with thermostatic control, roasting 2h at 700 DEG C, obtains carbon-alumina load copper oxide catalyst CuO/C-Al
2o
3, wherein CuO mass percentage is 20.6%.By prepared CuO/C-Al
2o
3catalyst loads in fixed bed reactors, and passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 370 DEG C is 1:10, is 0.5L/ (g in 0.3MPa, air speed
cath) with under the condition of reaction temperature 602 DEG C, the conversion ratio recording iso-butane is 51.5%, and selective isobutene is 84.3%, and after reaction 4h, the conversion ratio of iso-butane drops to 45.0%.
Embodiment 5
By Woelm Alumina, (specific area is about 200m
2/ g) impregnating pitch/acetone soln (pitch: alumina weight is 1.0:1), then after 120 DEG C of dry 12h, under 800 DEG C of nitrogen protections, roasting carbonization 1h, obtains C-Al
2o
3complex carrier, the content of carbon is 25.0wt%.3.41g copper chloride and 6.23g citric acid are dissolved in 533mL water, under stirring at room temperature, become solution, in above-mentioned solution, add prepared C-Al
2o
3complex carrier 4.77g, stirring and drying in 90 DEG C of waters bath with thermostatic control, roasting 2h at 700 DEG C, obtains carbon-alumina load copper oxide catalyst CuO/C-Al
2o
3, wherein CuO mass percentage is 25.0%.By prepared CuO/C-Al
2o
3catalyst loads in fixed bed reactors, and passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 370 DEG C is 1:10, is 0.5L/ (g in 0.3MPa, air speed
cath) with under the condition of reaction temperature 602 DEG C, the conversion ratio recording iso-butane is 46.5%, and selective isobutene is 88.9%, and after reaction 4h, the conversion ratio of iso-butane drops to 40.6%.
Embodiment 6
By Woelm Alumina, (specific area is about 210m
2/ g) flood sucrose solution (sucrose: alumina weight is 1.5:1), then after 120 DEG C of dry 12h, under 800 DEG C of nitrogen protections, roasting carbonization 1h, obtains C-Al
2o
3complex carrier, the content of carbon is 10.2wt%.2.42g copper nitrate and 2.10g citric acid are dissolved in 400mL water, stirring at room temperature becomes solution, in above-mentioned solution, add prepared C-Al
2o
3complex carrier 7.16g, stirring and drying in 60 DEG C of waters bath with thermostatic control, roasting 6h under 670 DEG C of blanket of nitrogen, obtains carbon-alumina load copper oxide catalyst CuO/C-Al
2o
3, wherein CuO mass percentage is 10.0%.By prepared CuO/C-Al
2o
3catalyst loads in fixed bed reactors, and passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 360 DEG C is 1:12, is 8L/ (g in 0.5MPa, air speed
cath) with under the condition of reaction temperature 620 DEG C, the conversion ratio recording iso-butane is 55.4%, and selective isobutene is 80.4%, and after reaction 5h, the conversion ratio of iso-butane drops to 49.9%.
Although the present invention with preferred embodiment openly as above; but embodiment is not for limiting the present invention, being anyly familiar with this those skilled in the art, without departing from the spirit and scope of the invention; can make various changes or retouch from working as, but same within protection scope of the present invention.What therefore protection scope of the present invention should define with the claims of the application is as the criterion.
Claims (8)
1. carbon-alumina load copper oxide catalyst, is characterized in that: the carrier that described catalyst comprises and active component, and described carrier is carbon-alumina composite carrier, and described active component is cupric oxide, and content is 4.0% ~ 25.0% of gross mass.
2. carbon according to claim 1-alumina load copper oxide catalyst, is characterized in that: described carbon-alumina composite carrier is porous material, and wherein the content of carbon in complex carrier is 5.0% ~ 25.0% of complex carrier quality.
3. a preparation method for carbon according to claim 1 and 2-alumina load copper oxide catalyst, is characterized in that comprising the following steps:
(1) by copper-containing compound and citric acid according to the mass ratio of copper simple substance and citric acid be the ratio mixing of 1:1.6 ~ 1:4.9, being dissolved in water and being made into copper simple substance mass concentration is the solution of 1.59 ~ 2.39g/L;
(2) in the solution prepared in step 1, add carbon-alumina composite carrier, additional proportion is 3.76 ~ 30.04g/g copper simple substance, stirs, dries, roasting, obtains carbon-alumina load copper oxide catalyst.
4. preparation method according to claim 3, is characterized in that: described copper-containing compound is copper nitrate, copper sulphate, Schweinfurt green or copper chloride.
5. preparation method according to claim 3, is characterized in that: in the roasting process of step 2, adopt inert atmosphere, and described inert atmosphere is for referring to O
2volumetric concentration lower than 0.1% high-purity N
2, high-purity Ar or high-purity He gas.
6. preparation method according to claim 3, is characterized in that: described carbon-alumina composite carrier adopts hydro carbons, carbohydrate, be carbon source containing carbon polymer or pitch, with vapour deposition or liquid impregnation and the process of carbonization carries out the surface-carbon-modified cathode of aluminium oxide.
7. carbon according to claim 1 or 2-alumina load copper oxide catalyst prepares the application in isobutene at dehydrogenation of isobutane, it is characterized in that: by described carbon-alumina load copper oxide catalyst filling in the reactor, control temperature of reactor at 540 ~ 620 DEG C, pressure 0.1 ~ 0.5MPa, pass into be preheated to 330 ~ 420 DEG C, the ratio of amount of substance is iso-butane and the carbon dioxide mix gas of 1:5 ~ 1:12, air speed is 0.5 ~ 8L/ (g
cath).
8. application according to claim 7, is characterized in that: described reactor is fixed bed reactors, fluidized-bed reactor or moving-burden bed reactor.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673977A (en) * | 2016-12-07 | 2017-05-17 | 大连理工大学 | Catalyst for preparing acetaldehyde through direct dehydrogenation of ethyl alcohol as well as preparation method and application thereof |
| CN108144603A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | The catalyst of CO vapor phase method Synthesis of dimethyl carbonate and its preparation and application |
| CN110354858A (en) * | 2019-08-23 | 2019-10-22 | 湖南长岭石化科技开发有限公司 | A kind of alcoholic solvent Hydrobon catalyst of epoxidation reaction of olefines process and its preparation method and application |
| CN111298845A (en) * | 2018-12-12 | 2020-06-19 | 中国石油化工股份有限公司 | Preparation method of denitration catalyst carrier |
| CN114181033A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108144603A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | The catalyst of CO vapor phase method Synthesis of dimethyl carbonate and its preparation and application |
| CN106673977A (en) * | 2016-12-07 | 2017-05-17 | 大连理工大学 | Catalyst for preparing acetaldehyde through direct dehydrogenation of ethyl alcohol as well as preparation method and application thereof |
| CN106673977B (en) * | 2016-12-07 | 2019-06-07 | 大连理工大学 | A kind of ethyl alcohol direct dehydrogenation prepares the catalyst of acetaldehyde, preparation method and applications |
| CN111298845A (en) * | 2018-12-12 | 2020-06-19 | 中国石油化工股份有限公司 | Preparation method of denitration catalyst carrier |
| CN111298845B (en) * | 2018-12-12 | 2022-03-04 | 中国石油化工股份有限公司 | Preparation method of denitration catalyst carrier |
| CN110354858A (en) * | 2019-08-23 | 2019-10-22 | 湖南长岭石化科技开发有限公司 | A kind of alcoholic solvent Hydrobon catalyst of epoxidation reaction of olefines process and its preparation method and application |
| CN114181033A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Method for recovering methane from ethylene waste gas produced in preparation of ethylene through oxidative coupling of methane |
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Application publication date: 20151104 |