CN105080564A - Catalyst used for preparation of carbon monoxide by conversion of carbon dioxide and use method thereof - Google Patents
Catalyst used for preparation of carbon monoxide by conversion of carbon dioxide and use method thereof Download PDFInfo
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Abstract
The present invention relates to a catalyst used for preparation of carbon monoxide by conversion of carbon dioxide and a use method thereof, and mainly aims to solve the problems of low conversion rate at low temperature and more byproducts of the catalyst in the prior art. The catalyst used for preparation of carbon monoxide by conversion of carbon dioxide comprises the following components by weight: 2% to 30% of an oxide of Mn, 0.5% to 10% of at least one oxide of Ce or La, 0.5% to 5% of a Cu oxide, 1% to 5% of an alkali metal, and 50% to 96% of a composite carrier, wherein the composite carrier comprises 5% to 39% of ZnO and 61% to 95% of Al2O3, by the technical scheme, the problem is well solved, when the catalyst is used in reaction for preparation of carbon monoxide by conversion of carbon dioxide, the catalyst has the advantages of high conversion rate at low temperature, and high selectivity of the target product, and can be used in industrial production for preparation of carbon monoxide by conversion of carbon dioxide.
Description
Technical field
The invention belongs to carbon dioxide conversion and utilize field, relate generally to a kind of catalyst for carbon dioxide conversion carbon monoxide and using method thereof.
Background technology
Carbon dioxide is main greenhouse gases, is the arch-criminal causing global warming, be also the carbon resource that can be used enriched very much, but current utilization rate only has about 1% simultaneously.2011, global CO
2total emission volumn 31,000,000,000 tons, wherein China CO
2total emission volumn reaches 8,200,000,000 tons, ranks first in the world.Exploitation CO
2the technology such as trapping, storage, trans-utilization will be the targets that global chemist is pursued jointly.Along with CO
2the greenhouse effects that a large amount of discharge causes are day by day serious, CO
2chemical conversion and research on utilization more and more active, wherein reverse water-gas-shift reaction (CO
2+ H
2=CO+H
2o, referred to as RWGS) be considered to one of reaction having application prospect most.
A large amount of greenhouse gases can be changed into synthesis gas by reverse water-gas-shift reaction (RWGS), and recycling synthesis gas goes the downstream chemical products preparing a series of high added value.In addition, except with natural gas, coal, heavy oil and residual oil etc. for raw material is produced except synthesis gas, RWGS is one and novel eco-friendlyly prepares synthesis gas route.Therefore from the angle that global carbon and carbon resource utilize, the most stable state CO of carbon
2the carbon resource that the mankind can utilize finally can be converted into, such as methyl alcohol, methane etc. by RWGS technique and catalyst technology.
Reverse water-gas-shift reaction is the endothermic reaction, and high temperature is conducive to generating CO, but too high reaction temperature not only can cause high energy consumption, and also higher to the requirement of reaction material.Usual scope is at 400 DEG C ~ 600 DEG C.When temperature is higher than 600 DEG C, energy consumption is very high, and economical in reaction is poor.Reverse water-gas-shift reaction is equal-volume reaction, and therefore the impact of pressure on reaction is less, but in order to improve reaction rate, suitably increases certain pressure.
In order to improve the selective of CO, its side reaction will be suppressed as best one can.The main side reaction of reverse water-gas-shift reaction is CO
2methanation (CO
2+ 4H
2=CH
4+ 2H
2o).Suppress CO
2methanation side reaction is mainly started with from the following aspects: a) temperature, and this reaction is strong exothermal reaction, raised temperature, and balance is moved to the left, and high temperature is conducive to suppressing CO
2methanation; B) pressure, this reaction is volume-diminished reaction, and increase pressure, balance moves right, and high pressure will promote CO
2methanation side reaction; C () hydrogen-carbon ratio, reduces hydrogen-carbon ratio, methane selectively reduces, and is conducive to suppressing CO
2methanation reaction.
At present, also there is dispute in the reaction mechanism of Reversed Water-gas Shift, the mechanism that main existence three is possible.First redox mechanism:
CO
2+2Cu→Cu
2O+CO(1)
H
2+Cu
2O→2Cu+H
2O(2)
Reaction (1) is oxidation step, and speed is slow; Reaction (2) is reduction step, and speed is fast, and therefore reacting (1) is rate determining step, and Cu is CO
2activated centre.Second mechanism is formates decomposition mechanism:
H
2→2H·
CO
2+H·→COOH·
COOH·→CO+OH·
OH·+H·→H
2O
3rd mechanism is Lacking oxygen mechanism:
The feature of this mechanism adopts Lacking oxygen to deactivate CO
2, the oxygen vacancy concentration of catalyst, oxygen migration ability and catalytic activity are closely related.
Catalyst for Reversed Water-gas Shift mainly contains copper-based catalysts, nickel-base catalyst, noble metal catalyst and other new catalytic material etc.Copper-based catalysts due to heat endurance poor, easily sintering and oxidized, therefore inapplicable pyroreaction [see Appl.Catal.A:Gen.2004,257,97-106].And Ni is catalyst based usually can as methanation catalyst, therefore when it is as Reversed Water-gas Shift catalyst, be easy to generate by-product CH
4, should avoid using this metallic element of Ni.Noble metal catalyst due to cost higher, and at high temperature easy-sintering and inactivation.
Adopt Reversed Water-gas Shift, CO
2being converted to CO is a CO having very large application potential
2trans-utilization process.Early stage research work was reported, adopted Fe-Cr oxide catalyst to be used for this reaction, but weak point to be methanation side reaction comparatively serious, the interpolation of Cr element is also have negative effect to environment in addition.Patent WO9606064A1 have employed Zn-Cr/Al
2o
3catalyst and EP2175986A2 have employed chromium-aluminium oxide catalyst, all there is above-mentioned shortcoming.
The people such as JaHunKwak report single dispersing Pd/Al
2o
3reversed Water-gas Shift catalyst, points out that the function of Pd is that activation is dissociated H
2, and alumina catalyst support plays activation CO absorption
2effect, by add La also can play promote activation CO
2effect, but owing to adopting noble metal as active component, cost higher [see ACSCatal.2013,3,2094-2100].
Chinese patent CN101624186B proposes a kind of technique of two-stage reverse water-gas-shift reaction, have employed load C o, Ni, the catalyst of at least two kinds of elements in W, Mo, reaction temperature is higher than 580 DEG C, and it is selective not provide CO, because operation temperature is higher, cause energy consumption large.
European patent EP 742172 and EP737647 adopt methane steam reforming method to prepare containing CO, CO proposition is a kind of
2and H
2synthesis gas technical process in, by adopt adsorbent remove reverse water-gas-shift reaction produce water, use this process to need the stages such as absorption, decompression, regeneration, step is comparatively complicated.
LURGI of Germany develops CAMERE technique, namely utilizes Water gas shift/WGS back reaction by carbon dioxide methanol.But very low by the conversion ratio of carbon dioxide direct hydrogenation methanol, methanol yield be improved, just must increase circulating air flow.And the maximum feature of CAMERE technique is combined reverse water-gas-shift reaction device and methyl alcohol synthetic reactor, thus overcome low temperature CO
2the shortcoming of low conversion rate, greatly reduces the unstripped gas internal circulating load of reaction.
Korea National science and technology institute's catalyst test room also develops a kind of CAMERE methanol-fueled CLC new technology.In the process, inverse reaction device and methyl alcohol synthetic reactor arranged in series, CO
2/ H
2first in reverse shift reaction device, carry out water-gas reverse shift reaction generate CO and H
2o, its reaction condition be normal pressure, 600 DEG C ~ 700 DEG C, the catalyst of employing is ZnAl
2o
4.Enter methanol synthesis reactor after the gaseous product dehydration generated to generate.
At present, to the domestic rare report of research work of water-gas reverse shift reaction and catalyst, and the Korea Advanced Institute of Science and Technology laboratory addressed before having and LURGI etc. develop this catalyst, complete the batch run of 5kg/d scale at present abroad.
According to existing bibliographical information result, at a relatively high temperature (600 ~ 800 DEG C), CO
2conversion ratio can reach about 40%, and this has also proved RWGS is the endothermic reaction, is at high temperature conducive to balancing the reason moved right.Comprehensive above patent or bibliographical information, find all to deposit conversion ratio at low temperatures not high, the problem that by-product is more.
Summary of the invention
Technical problem to be solved by this invention is that under the catalyst low temperature existed in prior art, conversion ratio is not high, the problem that by-product is more, there is provided a kind of by the catalyst of carbon dioxide conversion carbon monoxide and using method thereof, when this catalyst is used for carbon dioxide conversion reaction of carbon monoxide, there is high, the selective good advantage of low temperature conversion rate.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
For a catalyst for carbon dioxide conversion carbon monoxide, by weight percentage, following component is comprised: the oxide of the Mn of (a) 2% ~ 30%; At least one oxide of Ce or La of (b) 0.5% ~ 10%; The oxide of the Cu of (c) 0.5% ~ 5%; The alkali metal of (d) 1% ~ 5%; The complex carrier of (e) 50% ~ 96%; Wherein complex carrier by weight percentage, comprises following component: the ZnO of (f) 5% ~ 39%; The Al of (g) 61% ~ 95%
2o
3.
In such scheme, by weight percentage, the oxide containing Mn is preferably 5% ~ 15%; Oxide containing Ce or La is preferably 1% ~ 5%; Oxide containing Cu is preferably 1% ~ 3%; Alkali metal preferred version is the one be selected from Li, Na, K or Cs; Alkali metal oxide is preferably 1% ~ 3%.
In technique scheme, complex carrier is preferably gahnite.
For a method for carbon dioxide conversion carbon monoxide, with carbon dioxide and hydrogen for unstripped gas, reaction temperature 400 ~ 580 DEG C, reaction pressure 1 ~ 3Mpa, H
2/ CO
2volume ratio (1.2 ~ 3): under 1 condition, unstripped gas and the catalyst exposure described in any one of claim 1 ~ 6 are obtained by reacting carbon monoxide.
In technique scheme, the preferable range of reaction temperature is 500 ~ 550 DEG C, and the preferable range of reaction pressure is 2 ~ 3Mpa, H
2/ CO
2volume ratio preferably (2.5 ~ 3): 1.
In technique scheme, the volume space velocity of unstripped gas is preferably 3000 ~ 6000h
-1, be more preferably 3600 ~ 5000h
-1.
The using method of catalyst of the present invention comprises the following steps:
(1) preparation is rich in the material gas mixture of carbon dioxide and hydrogen, its H
2: CO
2volume ratio is in 1.2 ~ 3:1 scope.
(2) material gas mixture described in is under 400 ~ 580 DEG C and 1 ~ 3Mpa, and reaction is carried out continuously, with the catalyst exposure containing Mn base oxide, material gas mixture is reacted, and produces carbon monoxide and steam.
(3) carbon monoxide of beds unreacted out unstripped gas and generation completely and steam are through supercooling, steam is made all to be condensed into water, then gas-liquid separator is passed through, be separated with reaction gas mixtures continuously, thus separation water outlet, obtain the admixture of gas containing the carbon monoxide generated and the complete carbon dioxide of unreacted and hydrogen.
(4) the gas part after Separation of Water is emptying, and as required, remainder recycling processing, mixes with virgin gas, then through above-mentioned steps, to improve the ratio of carbon monoxide in product.
Hydrogenation of carbon dioxide can be converted into carbon monoxide by the catalyst that the present invention uses, and reaction equation is:
CO
2+ H
2+ catalyst → CO+H
2o+ catalyst
CO
2conversion ratio computing formula is as follows:
CO
2conversion ratio=([CO]+[CH
4])/([CO]+[CO
2]+[CH
4])
CO selective calculation formula is as follows:
CO is selective=[CO]/([CO]+[CH
4])
Preformed catalyst, by XRF (XRF) quantitative analysis gained, before analysis, passes through and is ground into powder, then compressing tablet analysis by the constituent content of catalyst.
GHG carbon dioxide fully can be changed into the synthesis gas being rich in carbon monoxide and hydrogen by the inventive method, for the synthesis of carbon one unstripped gas of downstream chemical products.In addition, the reaction temperature that catalyst of the present invention and using method thereof adopt is lower, and below 600 DEG C, conversion ratio is high, is conducive to carbon dioxide discharge-reduction and utilizes carbon cycle to utilize.The present invention is by Optimized Matching surface Acid and basic sites (carbon dioxide adsorption mobilizing function) and metal center (H
2dissociate mobilizing function), make it at higher H
2under activation capacity prerequisite, there is higher carbon dioxide adsorption, activation capacity, thus realize higher CO
2conversion ratio.
Adopt the catalyst that such scheme prepares, reaction temperature 400 ~ 580 DEG C, reaction pressure 1 ~ 3Mpa, H
2/ CO
2volume ratio 1.2 ~ 3:1 condition under, CO
2conversion ratio is 45 ~ 55%, and close to the equilibrium conversion of this reaction, the selective of CO is more than 90%, CO compared to existing technology
2conversion ratio improves about 20 ~ 30%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Accompanying drawing explanation
Fig. 1 process chart of the present invention
1-flowmeter, 2-unstripped gas blending tank, 3-reactor, 4-heat exchanger, 5-cooler, 6-gas-liquid separator
I-hydrogen, II-carbon dioxide, III-virgin gas, IV-circulating air, V-water, VI-emptying
Carbon dioxide and hydrogen are after flowmeter, enter unstripped gas blending tank, by being equipped with the fixed bed reactors of catalyst of the present invention, from reactor gas out to cooler, then by gas-liquid separator, the gentle body of water outlet is separated, as required, a part is emptying, and a part of recyclegas reenters reactor through heat exchange and reacts.
Detailed description of the invention
[embodiment 1]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 6.8 grams, lanthanum nitrate 2.9 grams, Schweinfurt green 3.3 grams, lithium nitrate 5.1 grams, adding citric acid 1.5 grams, 60.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of above-mentioned complex carriers, maceration extract is evenly sprayed on carrier, after drying roasting, both obtains catalyst.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 550 DEG C and 2Mpa.Catalytic component (being recorded by XRF) and evaluation result are in table 1.
[embodiment 2]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 17.0 grams, lanthanum nitrate 14.6 grams, Schweinfurt green 3.3 grams, lithium nitrate 7.6 grams, adding citric acid 1.5 grams, 60.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of above-mentioned complex carriers, maceration extract is evenly sprayed on carrier, after drying roasting, both obtains catalyst.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 550 DEG C and 2Mpa.Catalytic component (being recorded by XRF) and evaluation result are in table 1.
[embodiment 3]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 34.0 grams, lanthanum nitrate 29.2 grams, Schweinfurt green 1.65 grams, lithium nitrate 5.1 grams.Adding citric acid 1.5 grams, 60.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of above-mentioned complex carriers, is evenly sprayed on carrier by maceration extract, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 550 DEG C and 2Mpa.Catalytic component (being recorded by XRF) and evaluation result are in table 1.
[embodiment 4]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 51.0 grams, lanthanum nitrate 8.76 grams, Schweinfurt green 6.6 grams, lithium nitrate 7.6 grams.Adding citric acid 1.5 grams, 60.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of above-mentioned complex carriers, is evenly sprayed on carrier by maceration extract, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Catalytic component (being recorded by XRF) and evaluation result are in table 1.
[embodiment 5]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 51.0 grams, cerous nitrate 29.2 grams, Schweinfurt green 9.9 grams, lithium nitrate 10.2 grams.Adding citric acid 1.5 grams, 70.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of above-mentioned complex carriers, is evenly sprayed on carrier by maceration extract, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Catalytic component (being recorded by XRF) and evaluation result are in table 1.
[embodiment 6]
The preparation of carrier: A-get and intend boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 76.5 grams, cerous nitrate 17.5 grams, Schweinfurt green 1.98 grams, lithium nitrate 10.2 grams.Adding citric acid 7.6 grams, 60.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of complex carriers, is evenly sprayed on carrier by maceration extract, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Catalytic component (being recorded by XRF) and evaluation result are in table 1.
[embodiment 7]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 95.6 grams, lanthanum nitrate 23.4, Schweinfurt green 16.5 grams, lithium nitrate 5.1 grams.Adding citric acid 7.6 grams, 70.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of complex carriers, is evenly sprayed on carrier by maceration extract, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Catalytic component (being recorded by XRF) and evaluation result are in table 1.
[embodiment 8]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 114.7 grams, lanthanum nitrate 14.6 grams, Schweinfurt green 8.3 grams, lithium nitrate 5.1 grams, ammonium metatungstate 0.1 gram.Adding citric acid 7.6 grams, 80.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of complex carriers, is evenly sprayed on carrier by maceration extract, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Catalytic component (being recorded by XRF) and evaluation result are in table 1.
[embodiment 9]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 114.7 grams, lanthanum nitrate 29 grams, Schweinfurt green 3.3 grams, lithium nitrate 25 grams, adding citric acid 5 grams, 80.0 grams, water, heating for dissolving, is stirred to and dissolves completely, take 100.0 grams of complex carriers, maceration extract is evenly sprayed on carrier, after drying roasting, both obtain catalyst.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Catalytic component (being recorded by XRF) and evaluation result are in table 1.
[embodiment 10]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 114.7 grams, lanthanum nitrate 1.5 grams, Schweinfurt green 6.5 grams, lithium nitrate 5.1 grams, adding citric acid 5 grams, 80.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of complex carriers, maceration extract is evenly sprayed on carrier, after drying roasting, both obtains catalyst.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Catalytic component (being recorded by XRF) and evaluation result are in table 1.
Table 1
the constituent content of catalyst is recorded by XRF
* represent and to calculate with the percentage by weight of the oxide of this element
[comparative example 1]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 3.4 grams, Schweinfurt green 1.7 grams, lithium nitrate 5.1 grams.Adding citric acid 7.6 grams, 70.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of complex carriers, is evenly sprayed on carrier by maceration extract, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Evaluation result is in table 2.
[comparative example 2]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 3.4 grams, lanthanum nitrate 2.9 grams, Schweinfurt green 1.7 grams, adding citric acid 7.6 grams, 60.0 grams, water, heating for dissolving, is stirred to and dissolves completely, take 100.0 grams of complex carriers, maceration extract is evenly sprayed on carrier, after drying roasting, both obtain catalyst.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Evaluation result is in table 2.
[comparative example 3]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 17 grams, lanthanum nitrate 2.9 grams, Schweinfurt green 34 grams, lithium nitrate 2.5 grams.Adding citric acid 7.6 grams, 60.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of complex carriers, is evenly sprayed on carrier by maceration extract, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Evaluation result is in table 2.
[comparative example 4]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 17 grams, lanthanum nitrate 5.8 grams, lithium nitrate 2.5 grams.Adding citric acid 7.6 grams, 60.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of complex carriers, is evenly sprayed on carrier by maceration extract, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Evaluation result is in table 2.
[comparative example 5]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, adds zinc nitrate 26 grams, then adds by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, and mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtain shaping complex carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 17 grams, lanthanum nitrate 5.8 grams, Schweinfurt green 34 grams, lithium nitrate 25 grams.Adding citric acid 7.6 grams, 60.0 grams, water, heating for dissolving, is stirred to and dissolves completely, takes 100.0 grams of complex carrier I, is evenly sprayed on carrier by maceration extract, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Evaluation result is in table 2.
[comparative example 6]
The preparation of carrier: by zinc nitrate 100 DEG C of dryings 18 hours, 600 DEG C of roastings obtain ZnO carrier in 5 hours.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 114.7 grams, lanthanum nitrate 29 grams, Schweinfurt green 3.3 grams, lithium nitrate 25 grams, adding citric acid 5 grams, 80.0 grams, water, heating for dissolving, is stirred to and dissolves completely.Take the ZnO carrier of 100 grams, maceration extract is evenly sprayed on carrier, after drying roasting, both obtain catalyst.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Evaluation result is in table 2.
[comparative example 7]
The preparation of carrier: A-get boehmite 200.0 grams, pore creating material methylcellulose 3.0 grams; B-water intaking 40 grams, then add by weight percentage containing the aqueous solution 10.0 grams of nitric acid 30%, mixed dissolution is even.B slowly added A and stirs, mediating after 40 minutes, 100 DEG C of dryings 18 hours after extruded moulding, 750 DEG C of roastings 5 hours, obtain shaping Al
2o
3carrier.
Vehicle element: get above-mentioned carrier in 170 DEG C of dry activation 4 hours, for subsequent use.
Maceration extract is prepared: take manganese acetate 114.7 grams, lanthanum nitrate 29 grams, Schweinfurt green 3.3 grams, lithium nitrate 25 grams, adding citric acid 5 grams, 80.0 grams, water, heating for dissolving, is stirred to and dissolves completely.Take the Al of 100 grams
2o
3carrier, is evenly sprayed at maceration extract on carrier, both obtains catalyst after drying roasting.
Catalyst is loaded fixed bed reactors, admixture of gas consist of CO
2=100ml/min, H
2=200ml/min beds operates, after reaction, through refrigerated separation water outlet under 580 DEG C and 2Mpa.Evaluation result is in table 2.
Table 2
the constituent content of catalyst is recorded by XRF
* represent and to calculate with the percentage by weight of the oxide of this element
[embodiment 9 ~ 14]
Take the catalyst selecting embodiment 6 to prepare, under different process operating condition, check and rate catalyst, appraisal result is in table 3.
Table 3
Claims (10)
1. for a catalyst for carbon dioxide conversion carbon monoxide, by weight percentage, comprise following component:
The oxide of the Mn of (a) 2% ~ 30%;
At least one oxide of Ce or La of (b) 0.5% ~ 10%;
The oxide of the Cu of (c) 0.5% ~ 5%;
The alkali metal of (d) 1% ~ 5%;
The complex carrier of (e) 50% ~ 96%;
Wherein complex carrier is by weight percentage, comprises following component:
The ZnO of (f) 5% ~ 39%;
The Al of (g) 61% ~ 95%
2o
3.
2. the catalyst for carbon dioxide conversion carbon monoxide according to claim 1, is characterized in that, in catalyst weight percent, the content of the oxide of Mn is 5% ~ 15%.
3. the catalyst for carbon dioxide conversion carbon monoxide according to claim 1, is characterized in that, in catalyst weight percent, the content of the oxide of Ce or La is 1% ~ 5%.
4. the catalyst for carbon dioxide conversion carbon monoxide according to claim 1, is characterized in that, in catalyst weight percent, the content of the oxide of Cu is 1% ~ 3%.
5. the catalyst for carbon dioxide conversion carbon monoxide according to claim 1, is characterized in that, in catalyst weight percent, alkali metal is the one in Li, Na, K or Cs.
6. the catalyst for carbon dioxide conversion carbon monoxide according to claim 1, is characterized in that, in catalyst weight percent, the content of alkali metal oxide is 1% ~ 3%.
7. for a method for carbon dioxide conversion carbon monoxide, with carbon dioxide and hydrogen for unstripped gas, reaction temperature 400 ~ 580 DEG C, reaction pressure 1 ~ 3Mpa, H
2/ CO
2volume ratio (1.2 ~ 3): under 1 condition, unstripped gas and the catalyst exposure described in any one of claim 1 ~ 6 are obtained by reacting carbon monoxide.
8., according to claim 7 for the method for carbon dioxide conversion carbon monoxide, it is characterized in that reaction temperature is 500 ~ 550 DEG C, reaction pressure is 2 ~ 3Mpa, H
2/ CO
2volume ratio (2.5 ~ 3): 1.
9. according to claim 7 for the method for carbon dioxide conversion carbon monoxide, it is characterized in that, described unstripped gas and catalyst exposure react and generate carbon monoxide and steam, by the carbon monoxide that generates and steam and unreacted unstripped gas through supercooling, steam is made all to be condensed into water, by gas-liquid separator, from air-flow, be separated water outlet, and obtain the admixture of gas containing carbon monoxide, carbon dioxide and hydrogen.
10. according to claim 9 for the method for carbon dioxide conversion carbon monoxide, it is characterized in that, an admixture of gas part containing carbon monoxide, carbon dioxide and hydrogen is emptying, and all the other recycle back after reactor mixes with fresh unstripped gas and continue to react.
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| CN107188175A (en) * | 2017-06-29 | 2017-09-22 | 李卫教 | A kind of carbon dioxide converts the device and method of carbon monoxide |
| CN107552056A (en) * | 2016-06-29 | 2018-01-09 | 中国石油化工股份有限公司 | Catalyst, the preparation method and its usage of hydrogenation of carbon dioxide carbon monoxide |
| US10675681B2 (en) | 2017-02-02 | 2020-06-09 | Honda Motor Co., Ltd. | Core shell |
| CN112705191A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing carbon monoxide and preparation method and application thereof |
| US11053598B2 (en) | 2017-02-16 | 2021-07-06 | Honda Motor Co., Ltd. | Method for producing core shell nanoparticles |
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| US11053598B2 (en) | 2017-02-16 | 2021-07-06 | Honda Motor Co., Ltd. | Method for producing core shell nanoparticles |
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