CN101642708B - Non-noble metal catalyst, preparation thereof and application thereof - Google Patents
Non-noble metal catalyst, preparation thereof and application thereof Download PDFInfo
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- CN101642708B CN101642708B CN2008100127331A CN200810012733A CN101642708B CN 101642708 B CN101642708 B CN 101642708B CN 2008100127331 A CN2008100127331 A CN 2008100127331A CN 200810012733 A CN200810012733 A CN 200810012733A CN 101642708 B CN101642708 B CN 101642708B
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Abstract
The invention discloses a non-noble metal catalyst, preparation and application thereof. The non-noble metal catalyst consists of a non-noble metal Co active component and a carrier, wherein the content of Co is 1 to 30 percent by weight; and the carrier is a carbon material having a nano structure, which is carbon nano tube, carbon nano fiber and mesoporous carbon molecular sieve or active carbon with regular pores. The preparation process comprises the following steps: dissolving compounds of all components in a solvent according to a proportion to form solution, then dispersing the carrier to the solution by using a mode of ultrasonic auxiliary oscillation, naturally drying the solution, and gradually heating and treating the dried substances to obtain the catalyst, wherein the catalyst is reduced by hydrogen under 473 to 773 K before using. The catalyst of the invention is used for the synthesis of oxygen-containing C2 compounds, can generate ethanol high selectively, has low methane selectivity, and keeps good stability.
Description
Technical field
The present invention relates to non-precious metal catalyst, relate in particular to the cobalt-based multicomponent catalyst and preparation and the application that support with material with carbon element by synthesis gas preparation carbon two oxygenatedchemicals.
Background technology
Along with the minimizing day by day of petroleum resources, the coal that reserves are abundant and effective utilization of natural gas resource more and more come into one's own.The valid approach the most of coal and gas utilization is the organic compound through synthesis gas system high added value, the synthetic industrialization of methyl alcohol at present, yet C
2Oxygenatedchemicals is the product that economic worth is arranged in the product most, in case can carry out suitability for industrialized production important economic benefit will be arranged.C such as ethanol, acetate and acetaldehyde for example
2Oxygenatedchemicals is an important chemical material.Ethanol still substitutes good additive and the fuel that organo-lead compound improves environment and improves octane number.
At first develop from the eighties initial stage U.S. Union Carbide Corp (UCC) and to prepare C at rhodium base catalyst from synthesis gas
2Since the oxygenatedchemicals process route, various countries actively develop this respect research in succession.A large amount of discovers, rhodium base catalyst can promote the CO hydrogenation to generate hydro carbons very effectively, methyl alcohol, and higher alcohols, acid, aldehyde etc. are considered to best up to now from synthesis gas preparation C
2The catalyst of oxygenatedchemicals.Yet,, greatly limited through C such as synthesis gas preparation ethanol because the price of rhodium is very expensive
2The large-scale application of oxygenatedchemicals in industry.Therefore, people never stop to seek cheap base metal active component to replace the effort of rhodium base catalyst.
Up to the present, the synthetic research work that is used for carbon two oxygenatedchemicals about non-precious metal catalyst all is based on the improvement of or fischer-tropsch synthetic catalyst performance synthetic to methyl alcohol.It is generally acknowledged that the Fe in the VIII metal, Co, Ni have the higher CO ability of dissociating, can think that all potential CO hydrogenation generates C
2Oxygenatedchemicals reactive activity component.(the US4122110 of France Petroleum Institute, US4291126) the Cu-Co-M catalyst system and catalyzing (M=Cr, Fe, V, Mn or rare earth metal etc.) that adopts alkali metal or alkaline-earth metal to promote, developed new technology by synthesis gas system oxygenatedchemicals, except that methyl alcohol, can generate the higher alcohols product of more amount.Chang etc. (US4440668) find that the Cu-Co-Zr catalyst of three components can change into higher alcohol with synthesis gas, but product is still based on methyl alcohol.Uchiyama etc. (S.Uchiyama, Y.Obayashi, M.Shibata, T.Uchiyama, N.Kawata, T.Konishi, J.Chem.Soc.Chem.Commun., 1985,1071) find the Ni-TiO with the coprecipitation preparation
2Catalyst has higher CO hydrogenation activity, and the interpolation of Cu and Na can promote the generation of alcohol compounds such as ethanol, propyl alcohol.Miller etc. (US5096688) change into higher alcohol by two continuous processes with synthesis gas, use the cobalt of alkali metal promotion and the copper-based catalysts that alkaline-earth metal promotes respectively, but course of reaction have produced a large amount of CO
2After the nineties, Chuang etc. (S.S.C.Chuang, S.I.Pien, J.Catal.1991,128,569) find to use Na
2CO
3Co-precipitation Mn (NO
3)
2And Ni (NO
3)
2The Na-Mn-Ni catalyst of preparation has the activity of higher CO hydrogenation system acetaldehyde.Matsuzaki etc. (T.Matsuzaki, T.Hanaoka, K.Takeuchi, H.Arakawa, Y.Sugi, K.Wei, T.Dong, M.Reinikainen, Catal.Today, 1997,36,311) have reported and have used Co
2(CO)
8Co/SiO as the preparation of cobalt source
2Catalyst is to synthetic C
2Oxygenatedchemicals has activity, and finds to add a certain amount of alkali metal in the catalyst or alkaline-earth metal can suppress the generation of hydrocarbon, thereby makes C
2The selectivity of oxygenatedchemicals is improved.Aquino etc. (Catal.Today 2001,65 for A.D.de Aquino, A.J.Gomez Cobo, 209) then only when the reaction beginning, just have higher higher alcohol selectivity with the Al-Co-Cu-Na catalyst of coprecipitation preparation.Hayashi etc. (H.Hayashi, L.Z.Chen, T.Tago, M.Kishida, K.Wakabayashi, Appl.Catal.A, 2002,231,81) adopt the Fe/SiO of prepared with microemulsion reactor
2Catalyst has higher CO hydrogenation system C
2The activity of oxygenatedchemicals, but methane selectively is higher.
Summary of the invention
The object of the present invention is to provide a kind of non-precious metal catalyst and its production and application, it can be used for by synthesis gas preparation C
2Oxygenatedchemicals, this catalyst can generate C by highly selective
2Oxygenatedchemicals, and can significantly reduce the selectivity of methane, and also stability is better.
For achieving the above object, the technical solution used in the present invention is:
A kind of non-precious metal catalyst is made up of active component base metal Co and carrier, and the weight content of Co is 1～30%; Described carrier is the material with carbon element with nanostructured, and it is CNT, carbon nano-fiber, have the meso-porous carbon molecular sieve or the activated carbon in regular duct.
Described CNT is SWCN or multi-walled carbon nano-tubes; For SWCN, internal diameter is at 0.2～2nm, and external diameter is between 0.5～3nm; For multi-walled carbon nano-tubes, internal diameter is at 0.5～120nm, and external diameter is between 2～200nm; Described carbon molecular sieve is mesoporous carbon CMK-3; Described activated carbon is Vulcan XC-72
(Cabot Corp.).
Nano-carbon material described in the present invention is good with CNT, and caliber is between 2～200nm (o.d.) and 0.5～120nm (i.d.), and specific area is at 50～1200m
2Between/the g.
Active component of the present invention can also contain M and/or N except Co, wherein M is one or both among Mg, Ca, Sr, the Ba; N is one or both among Li, Na, K, Rb, the Cs; Its weight content in catalyst is M 1～30%, and N 0.01～10%.
Described Preparation of catalysts:
1) with material with carbon element 120～140 ℃ of oil baths backflow 10～14h in concentration 50～68wt.% nitric acid, filtration, water washing are filtered and are washed and can carry out according to conventional method to neutral; After the washing with product in 40～60 ℃ of baking ovens dry 12～24 hours;
CNT is used as the carrier of catalyst after nitric acid treatment; CNT shows good hydrophilicity after nitric acid treatment, in most of solvents such as soluble in water, alcohol.
Through after this strong oxidizing property acid treatment, the CNT two ends mouth of pipe is opened, and carbon nano tube structure still is kept perfectly simultaneously.In addition, the carbon tube wall has also been gone up oxygen-containing functional group by modification, can keep good hydrophily.
2) in proportion the soluble compound of aequum active component is dissolved in the solvent, wiring solution-forming is as the precursor mixed solution of preparation catalyst;
The active component presoma that is adopted among the present invention, be soluble in/can be water-soluble, the compound of alcohol or organic solvent.Described soluble compound can be the nitrate or the chloride of active component, and solvent for use is one or both in the methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol in water or the nonaqueous solvents.
3) with 1) in the material with carbon element of gained immerse 2) contain in the solution of active component soluble compound, the weight ratio of material with carbon element and solution is between 1: 10～1: 2000; After fully stirring more than 1 hour or 1 hour, mixed liquor is added the mode that supersonic oscillations or magnetic agitation add supersonic oscillations in mechanical agitation handle 1～10h, obtain mixture;
The mode that the present invention utilizes the auxiliary vibration of ultrasonic wave is scattered in carrier height in the solution of organic solvents such as the aqueous solution or methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol; The frequency range of supersonic oscillations is 15～100kHz; The mixing speed of mechanical agitation or magnetic agitation is 50～500rpm;
Supersonic oscillations can make the carbon pipe disperse, and the impurity such as air in the carbon pipe are diffused out, thereby the aqueous solution of metal ion enters into carbon pipe tube chamber under capillary force.And the huge specific surface of carbon pipe makes its strong trend that mutual gathering is arranged, so system is in the thermodynamic instability state, and the sonic oscillation of long period can cause the flocculation of carbon pipe to be reunited; Machinery or magnetic agitation can make the mixing in the big zone of solution, avoid the generation of carbon pipe flocculation.Therefore ultrasonic wave remedies mutually in conjunction with the effect that machinery (or magnetic force) stirs the two, can access the homogeneous mixture system that carbon pipe and active component reach the molecular level level.In the formed catalyst mother liquor, active component ion, solvent molecule and CNT reach other even dispersion of molecular level;
4) with 3) in the mixture solution of gained under stirring acutely, equably, air dry at room temperature; In 50～60 ℃ of temperature ranges, keep more than 3 hours or 3 hours then; The crystallization water of interior solution of CNT and predecessor is all slowly evaporated fully, avoid the interior solute of carbon pipe because of outside the follow-up heating discharger.
5) with 4) in the product of gained be raised to 110～140 ℃ with the heating rate of 0.2～2 ℃/min from room temperature, kept 10～12 hours, must catalyst prod.
Described non-precious metal catalyst is used for by synthesis gas preparation carbon two oxygenatedchemicals; Catalyst provided by the invention is applicable to synthetic C
2Oxygenatedchemicals; Reacting gas is a synthesis gas, H
2And the ratio of CO is between 1 to 3.5, and the air speed (GHSV) that is suitable for can be at 1000h
-1To 20000h
-1Change; The pressure that is suitable for changes between can be from 1Mpa to 10MPa; The operation temperature that is suitable for is 200 ℃ to 320 ℃;
Before application, be preferably in the hydrogen and under 200～500 ℃, reduced 3～5 hours.
The method for preparing catalyst that CNT provided by the present invention supports makes full use of the capillary force of CNT, with the soluble compound solution of active component, in the pipeline that is siphoned into CNT as much as possible.
In the catalyst of the present invention's preparation, particles of active components can be distributed in the tube chamber of CNT in a large number.
The catalyst that is made by the present invention has higher C
2The oxygenatedchemicals space-time yield; Be used for C
2Synthesizing of oxygenatedchemicals can generate ethanol by highly selective,
The catalyst that is made by the present invention has very high ethanol selectivity.
The catalyst that is made by the present invention has lower methane selectively.
The catalytic performance of the catalyst that is made by the present invention is highly stable.
Description of drawings
Fig. 1 is the C of catalyst under different temperatures that CNT and SBA-15 support
2Oxygenatedchemicals synthetic reaction performance is collection of illustrative plates, i.e. catalyst B and the D C under different temperatures relatively
2Oxygenatedchemicals synthetic reaction performance.
The specific embodiment
Give further instruction below by example to feature of the present invention:
Embodiment 1: Preparation of catalysts
(CNTs supports reactive metal on the o.d.10～20nm, i.d.4～8nm) and prepares catalyst at CNT.The percentage composition of Co and K is 10% and 0.5% in the catalyst.Concrete preparation method and active testing step are as follows:
The original CNT i.d.4 of 3g～8nm adding is filled in the there-necked flask of 150ml 68wt.% nitric acid, 140 ℃ of oil bath backflow 14h, magnetic agitation prevents bumping simultaneously.Filter then, be washed till neutrality with deionized water.With product in 60 ℃ of baking ovens dry 24 hours, note was CNT1 at last.Tem observation finds that nearly all carbon pipe mouth of pipe all is opened.
Contain 0.1g Co, the Co (NO of 0.05g Sr and 0.005g K with what prepare
3)
2, Sr (NO
3)
2And KNO
3Aqueous solution, (600W, 23KHz 2h) add under the mode of magnetic agitation and are distributed in the mixed solution, and magnetic agitation is to bone dry, then with the heating rate to 140 of 1 ℃/min ℃ and keep standby after 12 hours in supersonic oscillations with 1g CNT1.The Sr weight loading of this catalyst is 5%,, be labeled as catalyst A.Equally, preparation Sr weight loading is 15%, 20%, is labeled as catalyst B and C.
Embodiment 2: the evaluation I of catalyst activity
Be reflected in fixed bed (internal diameter is the 316L of the 7mm) reactor and carry out, the each loading amount of catalyst is 0.3g, in pure hydrogen atmosphere 350 ℃ the reduction 5 hours, be cooled to reaction temperature after, switch to synthesis gas and react.Gas-phase product adopts cold water to absorb the back off-line analysis with the online detection of gas-chromatography, product liquid.Concrete outcome is as shown in table 1, can see, and catalyst A, B, C all show high C
2The oxygenatedchemicals selectivity, and methane selectively is also very low.Especially catalyst C, under 250 ℃ of conditions, C
2The selectivity of oxygenatedchemicals is up to 87.06%.
Table 1. catalyst A, the reactivity worth of B and C
Reaction condition: reaction pressure 3MPa, H
2/ CO=2, air speed is 12,000h
-1
Embodiment 3: the evaluation II of catalyst activity
In fixed bed reactors, pack into 0.3g catalyst A or B, reaction condition is undertaken by example 2, and the reactivity worth of catalyst is listed in the table 2 with the variation of reaction temperature.Along with the raising of reaction temperature, the CO conversion ratio and the C of catalyst
2The space-time yield of oxygenatedchemicals increases gradually.Under same temperature, the activity of catalyst B is better than catalyst A, for example, at 320 ℃, on the catalyst A, C
2The space-time yield of oxygenatedchemicals is 101.51g/kg-cath, and on the catalyst B, then is 112.19g/kg-cath.
Table 2. catalyst A and the B reactivity worth under the differential responses temperature
Reaction condition: reaction pressure 3MPa, H
2/ CO=2, air speed is 12,000h
-1
Comparative example 1:
With original CNT i.d.4～8nm 110 ℃ of oil bath backflows of 37wt.% nitric acid 5h, filtration, deionized water are washed till neutrality.With product in 60 ℃ of baking ovens dry 24 hours, note was CNT2 at last.Weak condition is handled the carbon pipe that obtains like this, has kept the complete of the mouth of pipe.Therefore, during the preparation catalyst, active component can not be filled in the tube chamber, can only be at the outer surface of carbon pipe.
Adopt immersion process for preparing CATALYST Co SrK/CNT2.The activity of such catalysts evaluation method all is same as embodiment 2,3.By synthesis gas preparation C
2The reactivity worth of the catalyst of oxygenatedchemicals such as table 3 and table 4: find CATALYST Co SrK/CNT2 under the same conditions, if it is active in CoSrK/CNT1's.For example, the Sr loading was all 15% o'clock, at 320 ℃, and on the CATALYST Co SrK/CNT1, C
2The space-time yield of oxygenatedchemicals is 112.19g/kg-cath, and on CoSrK/CNT2, C
2The space-time yield of oxygenatedchemicals only is 68.56g/kg-cath.As seen, when active component is filled into carbon pipe tube chamber, the activity of such catalysts better performances.
The reactivity worth of the CoSrK/CNT2 catalyst of the different Sr content of table 3.
Reaction condition: 310 ℃ of reaction temperatures, reaction pressure 3MPa, H
2/ CO=2, air speed is 12,000h
-1
The reactivity worth of table 4. CATALYST Co SrK/CNT2 (Sr content 15%) under different temperatures
Reaction condition: reaction pressure 3MPa, H
2/ CO=2, air speed is 12,000h
-1
Comparative example 2:
With SBA-15 (Jinlin University high-tech share Co., Ltd) is carrier, and preparation CATALYST Co SrK/SBA-15 (Sr content 15%) is labeled as catalyst D.The catalyst activity evaluation method all is same as embodiment 2,3.The reactivity worth of catalyst B and D is relatively seen Fig. 1 and table 5.As seen from Figure 1, the CO conversion ratio and the C of catalyst B
2The space-time yield of oxygenatedchemicals all is higher than catalyst D in 290～320 ℃ of scopes.As shown in Table 5, catalyst B equal much lower than catalyst D of the selectivity of methane in the product under the differential responses temperature.
The comparison of table 5. catalyst B and D selectivity of product under the differential responses temperature
Reaction condition: reaction pressure 3MPa, H
2/ CO=2, air speed is 12,000h
-1
Comparative example 3:
In the document once the report at SiO
2On the Co catalyst based (T.Matsuzaki, K.Tskeuchi, T.hanaoka, H.Arakawa, Y.Sugi, Catal.Taday, 1996,28,251 that support; T.Matsuzaki, T.Hanaoka, K.Takeuchi, H.Arakawa, Y.Sugi, K.Wei, T.Dong, M.Reinikainen, Catal.Today, 1997,36,311), its reactivity worth row are as table 6.As seen from table, the catalyst of bibliographical information (even having added noble metal component) is all than the C of the catalyst B among the present invention in the low-temp reaction scope
2The selectivity of oxygenatedchemicals, especially product ethanol is much lower.
The SiO of table 6. bibliographical information
2Support the catalyst based reactivity worth of Co
Reaction condition: CO/H
2/ Ar=30/60/10, reaction pressure 2.1MPa, GHSV=2000h
-1Precursor C o (N) represents Co (NO
3)
26H
2O, Co (A) represents Co (CH
3COO)
24H
2O, Co (CO) represents Co
2(CO)
8.
Claims (9)
1. a non-precious metal catalyst is characterized in that: be made up of active component and carrier; Described carrier is the material with carbon element with nanostructured, and it is CNT, carbon nano-fiber, have the meso-porous carbon molecular sieve or the activated carbon in regular duct;
Described active component contains base metal Co, also contains M and N, and the weight content of Co is 1～30% in the catalyst, and wherein M is Sr, and N is K; Its weight content in catalyst is M 1～30%, and N 0.01～10%;
Described catalyst adopts following process to prepare:
1) with material with carbon element 120～140 ℃ of oil baths backflow 10～14h in concentration 50～68wt.% nitric acid, filters, washs;
2) in proportion the soluble compound of aequum active component is dissolved in the solvent, wiring solution-forming is as the precursor mixed solution of preparation catalyst;
3) with 1) in the material with carbon element of gained immerse 2) contain in the solution of active component soluble compound, the weight ratio of material with carbon element and solution is between 1: 10～1: 2000; After fully stirring more than 1 hour or 1 hour, mixed liquor is added the mode that supersonic oscillations or magnetic agitation add supersonic oscillations in mechanical agitation handle 1～10h, obtain mixture;
4) with 3) in the mixture solution of gained under stirring acutely, equably, air dry at room temperature; In 50～60 ℃ of temperature ranges, keep more than 3 hours or 3 hours then;
5) with 4) in the product of gained be raised to 110～140 ℃ with the heating rate of 0.2～2 ℃/min from room temperature, kept 10～12 hours, must catalyst prod.
2. according to the described catalyst of claim 1, it is characterized in that: described CNT is SWCN or multi-walled carbon nano-tubes; For SWCN, internal diameter is at 0.2～2nm, and external diameter is between 0.5～3nm; For multi-walled carbon nano-tubes, internal diameter is at 0.5～120nm, and external diameter is between 2～200nm; Described carbon molecular sieve is mesoporous carbon CMK-3.
3. described Preparation of catalysts method of claim 1 is characterized in that:
1) with material with carbon element 120～140 ℃ of oil baths backflow 10～14h in concentration 50～68wt.% nitric acid, filters, washs;
2) in proportion the soluble compound of aequum active component is dissolved in the solvent, wiring solution-forming is as the precursor mixed solution of preparation catalyst;
3) with 1) in the material with carbon element of gained immerse 2) contain in the solution of active component soluble compound, the weight ratio of material with carbon element and solution is between 1: 10～1: 2000; After fully stirring more than 1 hour or 1 hour, mixed liquor is added the mode that supersonic oscillations or magnetic agitation add supersonic oscillations in mechanical agitation handle 1～10h, obtain mixture;
4) with 3) in the mixture solution of gained under stirring acutely, equably, air dry at room temperature; In 50～60 ℃ of temperature ranges, keep more than 3 hours or 3 hours then;
5) with 4) in the product of gained be raised to 110～140 ℃ with the heating rate of 0.2～2 ℃/min from room temperature, kept 10～12 hours, must catalyst prod.
4. according to the described Preparation of catalysts method of claim 3, it is characterized in that: the material with carbon element washing back of gained is in 40～60 ℃ of baking ovens dry 12～24 hours 1).
5. according to the described Preparation of catalysts method of claim 3, it is characterized in that: described soluble compound is the nitrate or the chloride of active component, and solvent for use is one or both in the methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol in water or the nonaqueous solvents.
6. according to the described Preparation of catalysts method of claim 3, it is characterized in that: the frequency range of described supersonic oscillations is 15～100kHz; The mixing speed of mechanical agitation or magnetic agitation is 50～500rpm.
7. according to the described Preparation of catalysts method of claim 3, it is characterized in that: described material with carbon element is a CNT, and the external diameter in the caliber is between 2～200nm and internal diameter 0.5～120nm, and specific area is at 50～1200m
2Between/the g.
8. described Application of Catalyst of claim 1, it is characterized in that: described non-precious metal catalyst is used for by synthesis gas preparation carbon two oxygenatedchemicals; H in the synthesis gas
2With the volume ratio of CO 1～3.5, the air speed 1000h that is suitable for
-1To 20000h
-1Change; The pressure that is suitable for changes between from 1Mpa to 10MPa; The operation temperature that is suitable for is 200 ℃ to 320 ℃.
9. described according to Claim 8 Application of Catalyst is characterized in that: described non-precious metal catalyst reduced under 200～500 ℃ 3～5 hours in hydrogen before application.
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| CN101898134B (en) * | 2010-07-19 | 2011-12-28 | 江南大学 | Liquid phase preparation method for carbon nano tube and cobalt oxide composite structure |
| CN102485331A (en) * | 2010-12-06 | 2012-06-06 | 中国石油化工股份有限公司 | Mesoporous carbon-supported composite metal oxide catalyst and preparation method thereof |
| CN102641737B (en) * | 2012-03-21 | 2016-08-17 | 中国科学院大连化学物理研究所 | A kind of CO hydrogenation is directly synthesized C2-C10the catalyst of straight chain mixing primary alconol and preparation method and applications |
| CN102872870A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing distillate oil co-production high alcohol with synthesis gas, preparation method and application |
| KR101724979B1 (en) * | 2012-12-13 | 2017-04-07 | 바스프 코포레이션 | Carbon bodies and ferromagnetic carbon bodies |
| CN104667930A (en) * | 2015-02-28 | 2015-06-03 | 长沙学院 | Magnetic mesoporous carbon-supported cobalt catalyst and preparation method and application of catalyst |
| CN109622004B (en) * | 2018-09-26 | 2020-05-29 | 同济大学 | Preparation method and application of iron-based metal/nitrogen/carbon composite material for electrocatalysis |
| CN109395719B (en) * | 2018-11-05 | 2021-10-12 | 江苏大学 | Method for controllably loading noble metal nano material on surface of multi-walled carbon nanotube |
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| CN101134164A (en) * | 2006-08-31 | 2008-03-05 | 中国石油化工股份有限公司 | Co-based fischer-tropsch synthesis catalyst and method for preparing the same |
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