CN104437585A - Copper oxide catalyst for preparing isobutene through isobutane dehydrogenation and preparation method and application of copper oxide catalyst - Google Patents
Copper oxide catalyst for preparing isobutene through isobutane dehydrogenation and preparation method and application of copper oxide catalyst Download PDFInfo
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Abstract
Provided is a copper oxide catalyst for preparing isobutene by isobutane dehydrogenation, which takes nitrogen doped mesoporous carbon as a carrier and comprises 2-20% by mass of copper oxide as an active component, preferably 5-15%, being balanced with nitrogen doped mesoporous carbon. The preparation method comprises the following steps: mixing a copper-containing compound and citric acid at a mol ratio of 1:0.5-1:3; dissolving by adding water to prepare a blue solution with the copper concentration of 0.2-2.2 mol/L; adding nitrogen doped mesoporous carbon at a ratio of 319-3898 grams of nitrogen doped mesoporous per mol of copper into the aqueous solution; stirring at a constant temperature, drying, and roasting; and to obtain obtaining the copper oxide catalyst. The catalyst is used for preparing isobutene by isobutane dehydrogenation through oxidation by carbon dioxide, the conversion rate of isobutane can reach 25-70%, and the selectivity of isobutene can reach 70-96%. The catalyst free of noble metal and highly toxic chromium metallic oxide is low in cost, environment-friendly, easy to prepare, and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of catalyst of preparing isobutene through dehydrogenation of iso-butane, what be specifically related to is copper oxide catalyst of the N doping mesoporous carbon-loaded of a kind of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane and its preparation method and application.
Background technology
Isobutene is a kind of important C4 compound, can be used for synthesizing polyisobutylene, butyl rubber, methacrylic acid, methyl tertiary butyl ether(MTBE) and ethyl tert-butyl ether (ETBE) etc.At present, industrial isobutene is mainly derived from the accessory substance in ethylene production.Along with the scale of isobutene downstream product utilizes, the contradiction of its inadequate resource will be more outstanding, be the most competitiveness technology solving isobutene shortage by preparing isobutene through dehydrogenation of iso-butane.
There is abundant iso-butane resource in China, current petroleum catalytic cracking, the C4 hydro carbons of raw material by-product per ton 0.1 ton, and be the device of 2,000,000 tons for yearly productive capacity, the annual production of C4 is 200,000 tons, and wherein iso-butane just accounts for 36%.Domestic iso-butane is mainly used as fuel and burns, and causes the significant wastage of resource.If the efficient Oxidative Dehydrogenation isobutene of iso-butane can be realized, by being not only conducive to the utilization of resource but also can market demands being met, significant to China's oil development of chemical industry.
Current business-like catalyst for preparing isobutene through dehydrogenation of iso-butane and device are all from abroad, and such technology domestic is also in the desk study stage.
Preparing isobutene through dehydrogenation of iso-butane mainly contains three kinds of techniques: (1) direct dehydrogenation; (2) dioxygen oxidation dehydrogenation; (3) carbon dioxide oxidative dehydrogenation.Industrialized preparing isobutene through dehydrogenation of iso-butane technique all adopts direct dehydrogenation technique at present, and this technique has higher iso-butane conversion ratio and selective isobutene, but reaction temperature is higher, and energy consumption is larger.Dioxygen oxidation dehydrogenating technology is not by the restriction of thermodynamical equilibrium, and reaction temperature is lower, but deep oxidation reaction easily occurs, and selective isobutene is lower.Dehydrogenation reaction and inverse water gas reaction are coupled together by carbon dioxide oxidative dehydrogenation process, and not by the restriction of thermodynamical equilibrium, reaction temperature is lower, and simultaneously due to the oxidisability that carbon dioxide is more weak, deep oxidation reaction not easily occurs, and selective isobutene is higher.Therefore exploitation carbon dioxide oxidation catalyst for preparing isobutene through dehydrogenation of iso-butane has become study hotspot in recent years.
Ni is used for the reaction of carbon dioxide oxidation dehydrogenation of isobutane by Ding etc. on activated carbon, and research finds that NiO is active specy, CO
2not only can consume the hydrogen atom that dehydrogenation of isobutane reaction produces, the carbon deposit of catalyst surface can also be suppressed, the life-span of extending catalyst, the activity decrease of 550 DEG C of reaction 1 h rear catalysts is mild, the conversion ratio of iso-butane and the selective of isobutene are respectively 48.0% and 86.8%(Journal of Molecular Catalysis A:Chemical, 315 volume 221st ~ 225 pages in 2010).Sun Guosong etc. have prepared the CrO of mesopore molecular sieve MSU-1 load
xcatalyst, and the reactivity worth having investigated its catalysis carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane, find activity and the isolated state Cr of catalyst
6+number relevant, the conversion ratio of 600 DEG C of iso-butanes and the selective of isobutene are respectively 59.2% and 66.8%(catalysis journal, the 32nd volume the 8th phase in 2011 1424th ~ 1429 pages).Patent US7094942 reports in reaction gas the impact on chromium-based catalysts catalyzing iso-butane alkane dehydrogenation reaction when adulterating oxygen and carbon dioxide, result shows that oxygen and carbon dioxide significantly can reduce the carbon distribution of catalyst surface as auxiliary agent, and when substituting oxygen with carbon dioxide, can improve the selective of isobutene, selective isobutene reaches as high as 94.3%.
Relative to conventional carriers, N doping mesoporous carbon, due to heteroatomic effect, makes carrier have polarity, and the deposition for metal oxide particle provides more avtive spot, thus improves the activity of catalyst.The Supported Pt Nanoparticles on nitrogen-doped carbon nanometer pipe such as Bian carries out cyclohexene hydrogenation reaction, find that the conversion ratio of the nitrogen-doped carbon nanometer pipe of load 20% platinum at 15 ~ 200 DEG C of cyclohexene is close to 100%(Journal of Physical Chemistry C, the 113rd volume the 20th phase in 2009 8668th ~ 8672 pages).Woods etc. prepare nitrogen-doped carbon nanometer pipe by thermal cracking acetonitrile, have studied the cathode oxidation reproducibility of nitrogen-doped carbon nanometer pipe and associating between 325 DEG C of dehydrogenating propane activity, think that redox active and oxidative dehydrogenation are active relevant, active sites is the pyridine nitrogen (Catalysis Letters, the 136th volume 1st ~ 8 pages in 2010) in the nitrogen at nitrogen-doped carbon nanometer pipe tube wall edge and carbon pipe.
Up to now, be used for carbon dioxide oxidation dehydrogenation of isobutane with N doping mesoporous carbon-loaded cupric oxide and have no bibliographical information.
Summary of the invention
The object of the invention is to the defect overcoming prior art, provide a kind of cheap, preparation method is simple, eco-friendly copper oxide catalyst and its preparation method and application for carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane.
The present invention adopts following technical scheme:
A copper oxide catalyst for preparing isobutene through dehydrogenation of iso-butane, is characterized in that, described catalyst is with N doping mesoporous carbon for carrier, and active component cupric oxide counts 2 ~ 20% by mass percentage, and all the other are N doping mesoporous carbon.
In described catalyst, cupric oxide mass percentage preferably 5 ~ 15%.
Prepare the method for above-mentioned catalyst, carry out in the following order:
(1) by the compound of cupric and citric acid be in molar ratio 1:0.5 ~ 1:3 ratio mixing, the amount concentration being made into copper material that is dissolved in water is 0.2 ~ 2.2 mol/L blue solution;
(2) in the aqueous solution of step (1) cupric, add N doping mesoporous carbon, constant temperature stirring and drying, roasting in the ratio of every mole of copper 319 ~ 3898 g N doping mesoporous carbon, obtain the copper oxide catalyst of described N doping mesoporous carbon-loaded.
In above-mentioned preparation method, the compound of cupric comprises copper nitrate, copper sulphate, Schweinfurt green and copper chloride; The temperature of constant temperature stirring and drying is 60 ~ 90 DEG C; Roasting is through 550 ~ 650 DEG C of roasting 2-5 hour at inert atmosphere; The inert atmosphere that wherein roasting is used refers to O
2volumetric concentration lower than 0.1% high-purity N
2, one in high-purity Ar and high-purity He gas.
Aforesaid N doping mesoporous carbon, nitrogen content 3 ~ 25wt%, BET specific surface area 1100 ~ 3200 m
2/ g, most probable pore size is 2.5 ~ 9.5 nm, pore volume is at 1.1 ~ 3.5 mL/g, mesoporous is 70 ~ 100%, and preferred N doping mesoporous carbon comprises CNT, the carbon nano rod of N doping, the ordered mesopore carbon of N doping, the unordered mesoporous carbon prepared by organic carbon hydrate, metal halide carbonization of N doping of N doping.
Catalyst provided by the invention is used for the method for carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane, by Catalyst packing of the present invention in the reactor, control temperature of reactor at 560 ~ 620 DEG C, pressure 0.1 ~ 1.2 MPa, pass into and be preheated to 330 ~ 460 DEG C, the ratio of amount of substance is iso-butane and the carbon dioxide mix gas of 1:3 ~ 1:10, the overall flow rate of gas is every gram of catalyst 3 ~ 8 mark l/h, carries out dehydrogenation reaction.
The reactor that carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane adopts can be fixed bed reactors, fluidized-bed reactor or moving-burden bed reactor.
Beneficial effect of the present invention is:
Cupric oxide is cheap, and the catalyst cost being active fraction preparation with it is lower.The present invention, from the avtive spot increasing catalyst support surface, adopts N doping mesoporous carbon to be carrier, increases the decentralization of copper oxide particle at carrier surface, thus improves the dehydrogenation of isobutane performance of catalyst.The loaded copper oxide catalyst that is carrier with N doping mesoporous carbon provided by the invention, can obtain higher iso-butane conversion ratio and higher selective isobutene, thus reach higher isobutene yield under lower reaction temperature; The conversion ratio of iso-butane can reach 25 ~ 70%, and selective isobutene can reach 70 ~ 96%, has good industrial applications prospect.
Describe the present invention below in conjunction with specific embodiment.
Detailed description of the invention
Embodiment 1:
1.82 g Schweinfurt greens (0.01 mol) and 1.05 g citric acids (0.005 mol) are dissolved in 50 mL water, au bleu solution under stirring at room temperature, in above-mentioned solution, add nitrogen content 3%, specific area is 3200 m
2/ g, most probable pore size are nitrogen-doped nanometer pipe 38.98 g of 2.5 nm, and at 60 DEG C of constant temperature stirring and dryings, under 550 DEG C of blanket of nitrogen, roasting 5 hours, obtains the copper oxide catalyst of nitrogen-doped carbon nanometer pipe load, and the content measuring wherein cupric oxide is 3%.
Loaded in fixed bed reactors by the copper oxide catalyst of prepared nitrogen-doped carbon nanometer pipe load, passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 330 DEG C is 1:3, is 5 L/ (g in 0.1 MPa, air speed
cath) with under the condition of reaction temperature 580 DEG C, reacting the conversion ratio recording iso-butane after 1 hour is 29.3%, and selective isobutene is 90.6 %.
Embodiment 2:
2.42 g copper nitrates (0.01 mol) and 2.10 g citric acids (0.01 mol) are dissolved in 18 mL water, au bleu solution under stirring at room temperature, in above-mentioned solution, add nitrogen content 12%, specific area is 2800 m
2/ g, most probable pore size are nitrogen-doped nanometer pipe 15.11 g of 3.6 nm, and at 70 DEG C of constant temperature stirring and dryings, under 600 DEG C of blanket of nitrogen, roasting 4 hours, obtains the copper oxide catalyst of N doping mesoporous carbon-loaded, and measuring wherein cupric oxide mass percentage is 5%.
Loaded in fixed bed reactors by the copper oxide catalyst of prepared nitrogen-doped carbon nanometer pipe load, passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 400 DEG C is 1:7, is 3 L/ (g in 0.1 MPa, air speed
cath) with under the condition of reaction temperature 560 DEG C, reacting the conversion ratio recording iso-butane after 1 hour is 25.7%, and selective isobutene is 95.1%.
Embodiment 3:
1.78 g copper sulphate (0.01 mol) and 4.20 g citric acids (0.02 mol) are dissolved in 9 mL water, au bleu solution under stirring at room temperature, in above-mentioned solution, add nitrogen content 18%, specific area is 2700 m
2/ g, most probable pore size are nitrogen-doped nanometer pipe 7.16 g of 3.9 nm, and at 80 DEG C of constant temperature stirring and dryings, under 600 DEG C of blanket of nitrogen, roasting 3 hours, obtains the copper oxide catalyst of nitrogen-doped carbon nanometer pipe load, and the content measuring wherein cupric oxide is 10%.
Loaded in fixed bed reactors by the copper oxide catalyst of prepared nitrogen-doped carbon nanometer pipe load, passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 400 DEG C is 1:8, is 5 L/ (g in 0.1 MPa, air speed
cath) with under the condition of reaction temperature 600 DEG C, reacting the conversion ratio recording iso-butane after 1 hour is 45.6%, and selective isobutene is 81.2%.
Embodiment 4:
3.41 g copper chlorides (0.02 mol) and 8.41 g citric acids (0.04 mol) are dissolved in 9 mL water, au bleu solution under stirring at room temperature, in above-mentioned solution, add nitrogen content 25%, specific area is 1900 m
2/ g, most probable pore size are nitrogen-doped nanometer pipe 7.16 g of 4.1 nm, and at 90 DEG C of constant temperature stirring and dryings, under 650 DEG C of blanket of nitrogen, roasting 2 hours, obtains the copper oxide catalyst of nitrogen-doped carbon nanometer pipe load, and the content measuring wherein cupric oxide is 15%.
Loaded in fixed bed reactors by the copper oxide catalyst of prepared nitrogen-doped carbon nanometer pipe load, passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 460 DEG C is 1:10, is 8 L/ (g in 1.2 MPa, air speed
cath) with under the condition of reaction temperature 620 DEG C, reacting the conversion ratio recording iso-butane after 1 hour is 69.2%, and selective isobutene is 70.6%.
Embodiment 5:
Be dissolved in 10 mL water by 4.83 g copper nitrates (0.02 mol) and 12.61 g citric acids (0.06 mol), stirring at room temperature au bleu solution, adds nitrogen content 10% in above-mentioned solution, and specific area is 1320 m
2/ g, most probable pore size are N doping ordered mesopore carbon 6.39 g of 4.3 nm, and at 80 DEG C of constant temperature stirring and dryings, under 600 DEG C of blanket of nitrogen, roasting 4 hours, obtains the copper oxide catalyst of N doping mesoporous carbon-loaded, and the content measuring wherein cupric oxide is 20%.
Loaded in fixed bed reactors by the copper oxide catalyst of prepared N doping mesoporous carbon-loaded, passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 400 DEG C is 1:6, is 5 L/ (g in 0.1 MPa, air speed
cath) with under the condition of reaction temperature 580 DEG C, reacting the conversion ratio recording iso-butane after 1 hour is 35.3%, and selective isobutene is 84.6%.
Embodiment 6:
Be dissolved in 12 mL water by 2.42 g copper nitrates (0.01 mol) and 2.10 g citric acids, stirring at room temperature au bleu solution, adds nitrogen content 15% in above-mentioned solution, and specific area is 1100 m
2/ g, most probable pore size are unordered N doping mesoporous carbon 10.57 g of 9.5 nm, and at 80 DEG C of constant temperature stirring and dryings, under 600 DEG C of helium-atmospheres, roasting 4 hours, obtains the copper oxide catalyst of N doping mesoporous carbon-loaded, and measuring wherein cupric oxide content is 15.9%.
Loaded in fixed bed reactors by the copper oxide catalyst of prepared N doping mesoporous carbon-loaded, passing into iso-butane and carbon dioxide gas mixture that the amount of substance ratio being preheated to 400 DEG C is 1:8, is 7 L/ (g in 0.6 MPa, air speed
cath) with under the condition of reaction temperature 610 DEG C, reacting the conversion ratio recording iso-butane after 1 hour is 53.6 %, and selective isobutene is 78.1 %.
Claims (10)
1. a copper oxide catalyst for preparing isobutene through dehydrogenation of iso-butane, is characterized in that: described catalyst is with N doping mesoporous carbon for carrier, and active component cupric oxide counts 2 ~ 20% by mass percentage, and all the other are N doping mesoporous carbon.
2. the copper oxide catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 1, is characterized in that: described cupric oxide counts 5 ~ 15% by mass percentage.
3. prepare the method for the copper oxide catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 1, it is characterized in that, described preparation method comprises the steps:
(1) by the compound of cupric and citric acid be the ratio mixing of 1:0.5 ~ 1:3 in molar ratio, the amount concentration that is made into copper material of being dissolved in water is the solution of 0.2 ~ 2.2 mol/L;
(2) in the aqueous solution of step (1) cupric, add N doping mesoporous carbon, constant temperature stirring and drying, roasting in the ratio of every mole of copper 319 ~ 3898 g N doping mesoporous carbon, obtain described copper oxide catalyst.
4. the method preparing the copper oxide catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 3, is characterized in that: the compound of described cupric is copper nitrate, copper sulphate, Schweinfurt green or copper chloride.
5. the method preparing the copper oxide catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 3, is characterized in that: the temperature of described constant temperature stirring and drying is 60 ~ 90 DEG C.
6. the method preparing the copper oxide catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 3, is characterized in that: described roasting is under an inert atmosphere, 550 ~ 650 DEG C of roasting 2-5 hour.
7. the method preparing the copper oxide catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 6, is characterized in that: described inert atmosphere refers to O
2volumetric concentration lower than 0.1% high-purity N
2gas, high-purity Ar gas or high-purity He gas.
8. the method preparing the copper oxide catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 3, is characterized in that: described N doping mesoporous carbon is the unordered mesoporous carbon prepared by organic carbon hydrate, metal halide carbonization of the CNT of N doping, the carbon nano rod of N doping, the ordered mesopore carbon of N doping or N doping.
9. the method preparing the copper oxide catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 3, is characterized in that: the nitrogen content 3 ~ 25% of described N doping mesoporous carbon, BET specific surface area 1100 ~ 3200 m
2/ g, most probable pore size is 2.5 ~ 9.5 nm, and pore volume is at 1.1 ~ 3.5 mL/g, and mesoporous is 70 ~ 100%.
10. the copper oxide catalyst of preparing isobutene through dehydrogenation of iso-butane according to claim 1 is used for the method for carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane, it is characterized in that: by described Catalyst packing in the reactor, control temperature of reactor at 560 ~ 620 DEG C, pressure 0.1 ~ 1.2 MPa, pass into and be preheated to 330 ~ 460 DEG C, the ratio of amount of substance is iso-butane and the carbon dioxide mix gas of 1:3 ~ 1:10, the overall flow rate of gas is every gram of catalyst 3 ~ 8 ls/h, carries out dehydrogenation reaction and obtains isobutene.
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| CN109745978A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
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