CN107552056A - Catalyst, the preparation method and its usage of hydrogenation of carbon dioxide carbon monoxide - Google Patents
Catalyst, the preparation method and its usage of hydrogenation of carbon dioxide carbon monoxide Download PDFInfo
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Abstract
The present invention relates to a kind of hydrogenation of carbon dioxide CO catalyst and preparation method, mainly solves to exist in the prior art the technical problem more than by-product methane.The present invention includes following components by using a kind of hydrogenation of carbon dioxide CO catalyst in terms of molfraction：A) 0.9~10 part of metal Zr element or Ti elements；B) 1~10 part of alkali earth metal；C) technical scheme of 0.1~5 part of metal Mn element or Fe elements, preferably solves the problem, in the industrial production available for hydrogenation of carbon dioxide preparing synthetic gas.
Description
Technical field
The invention belongs to hydrogenation of carbon dioxide to utilize field, relates generally to a kind of hydrogenation of carbon dioxide catalyzing carbon monoxide
Agent, preparation method and its usage.
Background technology
Carbon dioxide is main greenhouse gases, is the arch-criminal for causing global warming, while is also very rich
The rich carbon resource that can be used, but current utilization rate only has 1% or so.2011, global CO2Total emission volumn
31000000000 tons, wherein China CO2Total emission volumn ranks first in the world up to 8,200,000,000 tons.Develop CO2The technologies such as trapping, storage, trans-utilization
It will be target that global chemist is pursued jointly.With CO2Greenhouse effects getting worse caused by a large amount of discharges, CO2Change
Learn conversion and research on utilization is more and more active, wherein reverse water-gas-shift reaction (CO2+H2=CO+H2O, referred to as RWGS) recognized
To be one of reaction for most having application prospect.
Reverse water-gas-shift reaction (RWGS) can change into substantial amounts of greenhouse gases synthesis gas, recycle synthesis gas to go
Prepare a series of downstream chemical products of high added values.In addition, except being produced with natural gas, coal, heavy oil and residual oil etc. for raw material
Outside synthesis gas, RWGS is one and new environment-friendly prepares synthesis gas route.Therefore from global carbon and carbon resource
From the perspective of utilization, the most stable state CO of carbon2Mankind's energy can be eventually converted into by RWGS techniques and catalyst technology
The carbon resource enough utilized, such as methanol, methane etc..
Reverse water-gas-shift reaction is the endothermic reaction, and high temperature is advantageous to generate CO, but too high reaction temperature can not only be made
Into high energy consumption, and the requirement to reacting material is also higher.Usual scope is at 400 DEG C~600 DEG C.When temperature be higher than 600 DEG C, energy
Consumption is very high, and economical in reaction is poor.Reverse water-gas-shift reaction is to react in equal volume, therefore influence of the pressure to reaction is smaller,
But in order to improve reaction rate, suitably increase certain pressure.
In order to improve CO selectivity it is necessary to suppress its side reaction as best one can.The main side reaction of reverse water-gas-shift reaction
It is CO methanations (CO+3H2=CH4+H2O).Suppress methanation side reaction mainly from the following aspects to start with：A) temperature, this is anti-
It should be strong exothermal reaction, raise temperature, balance is moved to the left, and high temperature is advantageous to suppress CO2Methanation；B) pressure, the reaction are
Volume-diminished is reacted, and increases pressure, and balance moves right, and high pressure will promote CO2Methanation side reaction；(c) hydrogen-carbon ratio, hydrogen is reduced
Carbon ratio, methane selectively reduce, and are advantageous to suppress CO2Methanation reaction.These are all methanations of being disinthibited from process conditions
Reaction, goes to avoid the occurrence of methanation center and is only basic place from Catalyst Design angle.
At present, also there is dispute in the reaction mechanism of Reversed Water-gas Shift, be primarily present three possible mechanism.One is oxygen
Change reduction mechanism：
CO2+2Cu→Cu2O+CO (1)
H2+Cu2O→2Cu+H2O (2)
It is oxidation step to react (1), and speed is slow；It is reduction step to react (2), and speed is fast, therefore it is speed control to react (1)
Step processed, Cu CO2Activated centre.Second mechanism is formates decomposition mechanism：
H2→2H·
CO2+H·→COOH·
COOH·→CO+OH·
OH·+H·→H2O
3rd mechanism is Lacking oxygen mechanism：
The characteristics of mechanism, is deactivated CO using Lacking oxygen2, oxygen vacancy concentration, oxygen migration ability and the catalysis of catalyst
Activity is closely related.
Catalyst for Reversed Water-gas Shift mainly have copper-based catalysts, nickel-base catalyst, noble metal catalyst and its
Its new catalytic material etc..Copper-based catalysts are easily sintered and are oxidized because heat endurance is poor, therefore inapplicable pyroreaction
[referring to Appl.Catal.A:Gen.2004,257,97-106].And Ni bases catalyst can generally be used as methanation catalyst,
Therefore when it is as Reversed Water-gas Shift catalyst, it is easy to generate by-product CH4, should avoid using this metallic elements of Ni.
Noble metal catalyst because cost is higher, and at high temperature easy-sintering and inactivate.
Using Reversed Water-gas Shift, CO2It is a CO for having very big application potential to be converted to CO2Trans-utilization mistake
Journey.The research work of early stage was reported, was used for the reaction using Fe-Cr oxide catalysts, but weak point is methanation pair
Reaction is more serious, and the addition of Cr elements in addition is also to have negative effect to environment.Patent WO9606064A1 employs Zn-Cr/
Al2O3Catalyst and EP2175986A2 employ chromium-aluminium oxide catalyst, the shortcomings that above-mentioned all be present.
Ja Hun Kwak et al. report single dispersing Pd/Al2O3Reversed Water-gas Shift catalyst, it is indicated that Pd function is work
Dissolve from H2, and alumina catalyst support plays activation CO absorption2Effect, by add La can also play promotion activation CO2Make
With, but because using noble metal, as active component, cost is higher [referring to ACS Catal.2013,3,2094-2100].
Chinese patent CN101624186B proposes a kind of technique of two-stage reverse water-gas-shift reaction, employs load
The catalyst of at least two elements in Co, Ni, W, Mo, reaction temperature are higher than 580 DEG C, and do not provide CO selectivity, due to reaction
Operation temperature is higher, causes energy consumption big.
Wang etc. is [referring to Journal of Rare Earths, 2008,26 (1):66-70；Chemistry Letters,
2013,42:682-683] using 1wt%K modifications Co-CeO2Catalyst promotes CO2Absorption, has poisoned methanation activity position,
CH4Selectivity is down to 1%, but does not provide stability result.Because oxidation state Co is easily reduced into metal Co at high temperature, no
It can avoid producing methane.
Abolfazl etc. is [referring to Chinese Journal of Chemical Engineering, 2013,21 (9):
1007-1014；Journal of Nanoscience and Nanotechnology,2014,14(9):6841-6847；
Chemical Biochemical Engineering Quarterly,2013,27(3):275-278] it have studied Fe-Mo, Ni-
Mo and Co-Mo systems are respectively used to RWGS reactions, as a result find to form NiMoO4 and the phase structures of Fe2 (MoO4) 3 for being difficult to reduce
Be advantageous to improve the stability of catalyst, but for Co-Mo/Al2O3 systems, CO is selectively just down to 87% after 1h.
Grabowski etc. [referring to ACS catalysis, 2011,1:266-278] Ag/ is prepared for using coprecipitation
ZrO2 catalyst, find the carrier loaded Ag of Tetragonal+Catalyst forms species among formates, and dispersed Ag0 activity mutually solves
From ADSORPTION STATE CO2Produce surface C O and O species.Wang Luhui etc. [referring to CN103183346A] is used for RWGS using nickel cerium catalyst
Reaction, its CO2Conversion ratio is only 25%.
European patent EP 742172 and EP737647 propose it is a kind of using methane steam reforming method come prepare containing
CO、CO2And H2Synthesis gas technical process in, remove water caused by reverse water-gas-shift reaction by using adsorbent, make
It is complex stage, the step such as to need to adsorb, depressurize, regenerating with this process.
German LURGI develops CAMERE techniques, i.e., generates first by carbon dioxide using Water gas shift/WGS back reaction
Alcohol.But the conversion ratio that methanol is generated by carbon dioxide direct hydrogenation is very low, to improve methanol yield, must just increase circulating air
Flow.And the characteristics of CAMERE technique maximums is to combine reverse water-gas-shift reaction device with methyl alcohol synthetic reactor, so as to
Overcome low temperature CO2The shortcomings that conversion ratio is low, greatly reduce 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 CLCs new technology.In the work
In skill, inverse reaction device and methyl alcohol synthetic reactor arranged in series, CO2/H2Water-gas inverse transformation is carried out first in reverse shift reaction device
Reaction generation CO and H2O, its reaction condition are normal pressure, and 600 DEG C~700 DEG C, the catalyst used is ZnAl2O4.The gas of generation
Enter methanol synthesis reactor after product dehydration to generate.
At present, the domestic rare report of the research work to water-gas reverse shift reaction and catalyst, and foreign countries are already described before having
And Korea Advanced Institute of Science and Technology laboratory and LURGI etc. this catalyst is developed, completed 5kg/ at present
The batch run of d scales.
According to existing document report result, at a relatively high temperature (600~800 DEG C), CO2Conversion ratio is left up to 40%
The right side, it is the endothermic reaction that this, which has also proved RWGS, is advantageous to the reason that balance moves right at high temperature.In summary patent or text
Report is offered, discovery has the problem of by-product methane is more.
The content of the invention
One of technical problems to be solved by the invention are that hydrogenation of carbon dioxide carbon monoxide to be in the prior art present anti-
Technical problem in answering more than by-product methane, there is provided a kind of catalyst for hydrogenation of carbon dioxide carbon monoxide, the catalyst
During for hydrogenation of carbon dioxide reaction of carbon monoxide, there is the advantages of high CO is selective, and by-product methane is few.
The two of the technical problems to be solved by the invention are to provide a kind of with solving one of technical problem corresponding catalysis
The preparation method of agent.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
A kind of hydrogenation of carbon dioxide CO catalyst, in terms of molfraction, includes following components：A) 0.9~10
Part metal Zr elements and/or Ti elements；B) 1~10 part of alkali earth metal；C) 0.1~5 part of metal Mn element and/or Fe members
Element.
In above-mentioned technical proposal, in terms of molfraction, it is preferred that metal Zr and/or Ti content are 1~5 part.
In above-mentioned technical proposal, in terms of molfraction, it is preferred that Zr and Ti mol ratio (10：1)~(1：5), more preferably
, Zr and Ti mol ratio (5：1)~(1：2).
In above-mentioned technical proposal, in terms of molfraction, it is preferred that the content of alkaline-earth metal is 1~5 part.
In above-mentioned technical proposal, in terms of molfraction, it is preferred that metal Fe or Mn content are 0.1~1 part.
In above-mentioned technical proposal, the element selected from alkaline-earth metal is preferably at least one of Mg, Ca and Ba.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows, the system of catalyst of the present invention
Preparation Method comprises the steps of：
(1) the precursor salt water solution A of Zr elements and/or Ti elements, the wherein precursor salt of Zr elements and/or Ti elements are prepared
Preferably at least one of acetate, nitrate and sulfate；
(2) forerunner's saline solution B of at least one element selected from alkaline-earth metal is prepared；
(3) the precursor salt solution C of Mn elements and/or Fe elements is prepared, the wherein precursor salt of Mn elements and/or Fe elements is excellent
Elect at least one of acetate, nitrate as；
(3) A, B, C are mixed, uniform stirring, container and quick stirring, bath temperature is uniformly added drop-wise to precipitating reagent cocurrent
At 60~80 DEG C, pH value is controlled 8~9；
(4) mother liquor is isolated, will be dried after sediment progress hydro-thermal process, roasting obtains finished product.
To reach the object of the invention, drying mode does not specially require, it is preferred to use vacuum drying, dry temperature
Preferably 90~120 DEG C, the dry time is preferably 12~48 hours.The temperature of high-temperature roasting is preferably 650~1000 DEG C, roasting
The time of burning is preferably 5~15 hours.
The application method that catalyst of the present invention is used for hydrogenation of carbon dioxide carbon monoxide is as follows：
Using carbon dioxide and hydrogen as unstripped gas, in 550~600 DEG C of reaction temperature, reaction pressure is normal pressure~1MPa,
H2/CO2Volume ratio (1:1)~(3:And 6000~15000h of volume space velocity 1)-1Under the conditions of, unstripped gas connects with above-mentioned catalyst
Tactile reaction obtains carbon monoxide and vapor.The carbon monoxide of generation and the complete unstripped gas of vapor and unreacted are passed through
Cooler, gas-liquid separator, water outlet is separated, obtain the admixture of gas rich in carbon monoxide, carbon dioxide and hydrogen.
In above-mentioned technical proposal, the preferred scope of reaction pressure is normal pressure~0.5MPa, and the volume space velocity of unstripped gas is preferred
For 8000~12000h-1。
Catalyst of the present invention can be used for hydrogenation of carbon dioxide reaction of carbon monoxide, specific reaction equation
For：
CO2+H2→CO+H2O
CO2Conversion ratio (XCO2) and CO (SCO) selective calculation formula is as follows：
Catalyst of the present invention and preparation method thereof fully can change into GHG carbon dioxide rich in an oxygen
Change the synthesis gas of carbon and hydrogen, for synthesizing the downstream chemical products of high added value.In addition, catalyst of the present invention and its making
The reaction temperature used with method is relatively low, and below 600 DEG C, high conversion rate, stability is good.In order to improve conversion ratio, the present invention
Pass through Optimized Matching surface Acid and basic sites (carbon dioxide adsorption mobilizing function) and metal center (H2Dissociate mobilizing function), make it
In higher H2Under the premise of activation capacity, there is higher carbon dioxide adsorption, activation capacity, so as to realize higher CO2Conversion
Rate；In order to improve the stability of catalyst, the present invention, so as to form spinel active phase, improves catalyst by high-temperature process
Resistance to reduction, the high temperature strong reducing property hydrothermal condition of reverse water-gas-shift reaction can be resistant to.
The catalyst being prepared using above-mentioned technical proposal, in 550~600 DEG C of reaction temperature, reaction pressure normal pressure~
0.5Mpa, H2/CO2Volume ratio (1:1)~(3:And 6000~15000h of air speed 1)-1Under the conditions of, CO2Conversion ratio 43~
53%, CO are selectively more than 95%, catalyst continuous and steady operation 1000h non-inactivations.CO compared with prior art2Conversion ratio and
The stability of catalyst is significantly increased, and achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
[catalyst preparation]：429.3 grams of pin acid zirconium is weighed, 148 grams of magnesium nitrate, 4.1 grams of ferric nitrate, is dissolved in deionization respectively
In water, then it is well mixed, is configured to mixing salt solution；250 grams of ammonium carbonate is weighed, is configured to precipitant solution；By precipitating reagent
Solution and the uniform cocurrent of salting liquid are added drop-wise in three-necked flask, and quick stirring, control 60 DEG C of bath temperature, and pH value is adjusted to 8,
Stirring 12 hours, stands overnight.
[activation of catalyst]：By the solution after standing overnight, filtration washing is carried out, filter cake is then placed into water heating kettle and entered
Water-filling is heat-treated, 180 DEG C of hydro-thermal process temperature, 24 hours processing times.Then filtration washing is carried out again, will be deposited in 120
DEG C vacuum drying 12 hours, 800 DEG C be calcined 5 hours.
[evaluating catalyst]：Catalyst is loaded into fixed bed reactors, the composition of admixture of gas is CO2=333ml/
min,H2=667ml/min beds operate under 600 DEG C and 0.5Mpa, after reaction, by refrigerated separation water outlet.Evaluation
It the results are shown in Table 1.
[embodiment 2]
[catalyst preparation]：402 grams of titanium sulfate is weighed, 164 grams of calcium nitrate, 201.9 grams of ferric nitrate, is dissolved in deionization respectively
In water, then it is well mixed, is configured to mixing salt solution；200 grams of ammonium carbonate is weighed, is configured to precipitant solution；By precipitating reagent
Solution and the uniform cocurrent of salting liquid are added drop-wise in three-necked flask, and quick stirring, control 80 DEG C of bath temperature, and pH value is adjusted to 9,
Stirring 12 hours, stands overnight.
[activation of catalyst]：By the solution after standing overnight, filtration washing is carried out, filter cake is then placed into water heating kettle and entered
Water-filling is heat-treated, 180 DEG C of hydro-thermal process temperature, 36 hours processing times.Then filtration washing is carried out again, will be deposited in 120
DEG C vacuum drying 12 hours, 800 DEG C be calcined 5 hours.
[evaluating catalyst]：Catalyst is loaded into fixed bed reactors, the composition of admixture of gas is CO2=333ml/
min,H2=667ml/min beds operate under 600 DEG C and 0.5Mpa, after reaction, by refrigerated separation water outlet.Evaluation
It the results are shown in Table 1.
[embodiment 3]
[catalyst preparation]：42.9 grams of pin acid zirconium is weighed, 26.1 grams of barium nitrate, 50% 3.6 grams of manganese nitrate solution, is distinguished molten
In deionized water, then it is well mixed, is configured to mixing salt solution；250 grams of ammonium carbonate is weighed, is configured to precipitant solution；
Precipitant solution and the uniform cocurrent of salting liquid are added drop-wise in three-necked flask, and quick stirring, control 60 DEG C of bath temperature, pH value
Regulation is stirred 12 hours, stood overnight to 8.
[activation of catalyst]：By the solution after standing overnight, filtration washing is carried out, filter cake is then placed into water heating kettle and entered
Water-filling is heat-treated, 180 DEG C of hydro-thermal process temperature, 24 hours processing times.Then filtration washing is carried out again, will be deposited in 120
DEG C vacuum drying 12 hours, 800 DEG C be calcined 5 hours.
[evaluating catalyst]：Catalyst is loaded into fixed bed reactors, the composition of admixture of gas is CO2=333ml/
min,H2=667ml/min beds operate under 600 DEG C and 0.5Mpa, after reaction, by refrigerated separation water outlet.Evaluation
It the results are shown in Table 1.
[embodiment 4]
[catalyst preparation]：Weigh 386.1 grams of pin acid zirconium, 40.2 grams of titanium sulfate, 148 grams of magnesium nitrate, 4.1 grams of ferric nitrate,
It is dissolved in deionized water, is then well mixed respectively, is configured to mixing salt solution；250 grams of ammonium carbonate is weighed, is configured to precipitating reagent
Solution；Precipitant solution and the uniform cocurrent of salting liquid are added drop-wise in three-necked flask, and quick stirring, control bath temperature 60
DEG C, pH value is adjusted to 8, is stirred 12 hours, is stood overnight.
[activation of catalyst]：By the solution after standing overnight, filtration washing is carried out, filter cake is then placed into water heating kettle and entered
Water-filling is heat-treated, 180 DEG C of hydro-thermal process temperature, 24 hours processing times.Then filtration washing is carried out again, will be deposited in 120
DEG C vacuum drying 12 hours, 800 DEG C be calcined 5 hours.
[evaluating catalyst]：Catalyst is loaded into fixed bed reactors, the composition of admixture of gas is CO2=333ml/
min,H2=667ml/min beds operate under 600 DEG C and 0.5Mpa, after reaction, by refrigerated separation water outlet.Evaluation
It the results are shown in Table 1.
[embodiment 5]
[catalyst preparation]：Weigh 85.8 grams of pin acid zirconium, 321.6 grams of titanium sulfate, 234.9 grams of barium nitrate, ferric nitrate 4.1
Gram, it is dissolved in deionized water, is then well mixed respectively, is configured to mixing salt solution；250 grams of ammonium carbonate is weighed, is configured to sink
Shallow lake agent solution；Precipitant solution and the uniform cocurrent of salting liquid are added drop-wise in three-necked flask, and quick stirring, control bath temperature
60 DEG C, pH value is adjusted to 8, is stirred 12 hours, is stood overnight.
[activation of catalyst]：By the solution after standing overnight, filtration washing is carried out, filter cake is then placed into water heating kettle and entered
Water-filling is heat-treated, 180 DEG C of hydro-thermal process temperature, 24 hours processing times.Then filtration washing is carried out again, will be deposited in 120
DEG C vacuum drying 12 hours, 800 DEG C be calcined 5 hours.
[evaluating catalyst]：Catalyst is loaded into fixed bed reactors, the composition of admixture of gas is CO2=333ml/
Min, H2=667ml/min beds operate under 600 DEG C and 0.5Mpa, after reaction, by refrigerated separation water outlet.Evaluation
It the results are shown in Table 1.
[embodiment 6]
[catalyst preparation]：214.6 grams of pin acid zirconium is weighed, 130.5 grams of barium nitrate, 41 grams of ferric nitrate, 50% manganese nitrate is molten
3.6 grams of liquid, is dissolved in deionized water, is then well mixed, be configured to mixing salt solution respectively；250 grams of ammonium carbonate is weighed, is prepared
Into precipitant solution；Precipitant solution and the uniform cocurrent of salting liquid are added drop-wise in three-necked flask, and quick stirring, control water-bath
Temperature 60 C, pH value adjust to 8, stir 12 hours, stand overnight.
[activation of catalyst]：By the solution after standing overnight, filtration washing is carried out, filter cake is then placed into water heating kettle and entered
Water-filling is heat-treated, 180 DEG C of hydro-thermal process temperature, 24 hours processing times.Then filtration washing is carried out again, will be deposited in 120
DEG C vacuum drying 12 hours, 800 DEG C be calcined 5 hours.
[evaluating catalyst]：Catalyst is loaded into fixed bed reactors, the composition of admixture of gas is CO2=333ml/
min,H2=667ml/min beds operate under 600 DEG C and 0.5Mpa, after reaction, by refrigerated separation water outlet.Evaluation
It the results are shown in Table 1.
[embodiment 7]
[catalyst preparation]：Weigh 214.6 grams of pin acid zirconium, 130.5 grams of barium nitrate, 20.5 grams of ferric nitrate, 50% manganese nitrate
18 grams of solution, is dissolved in deionized water, is then well mixed, be configured to mixing salt solution respectively；250 grams of ammonium carbonate is weighed, is matched somebody with somebody
Precipitant solution is made；Precipitant solution and the uniform cocurrent of salting liquid are added drop-wise in three-necked flask, and quick stirring, control water
60 DEG C of bath temperature, pH value adjust to 8, stir 12 hours, stand overnight.
[activation of catalyst]：By the solution after standing overnight, filtration washing is carried out, filter cake is then placed into water heating kettle and entered
Water-filling is heat-treated, 180 DEG C of hydro-thermal process temperature, 24 hours processing times.Then filtration washing is carried out again, will be deposited in 120
DEG C vacuum drying 12 hours, 800 DEG C be calcined 5 hours.
[evaluating catalyst]：Catalyst is loaded into fixed bed reactors, the composition of admixture of gas is CO2=333ml/
min,H2=667ml/min beds operate under 600 DEG C and 0.5Mpa, after reaction, by refrigerated separation water outlet.Evaluation
It the results are shown in Table 1.
[embodiment 8]
[catalyst preparation]：Claim 40.2 grams of titanium sulfate, 26.1 grams of barium nitrate, 20.5 grams of ferric nitrate, 50% manganese nitrate solution
18 grams, it is dissolved in deionized water, is then well mixed respectively, is configured to mixing salt solution；250 grams of ammonium carbonate is weighed, is configured to
Precipitant solution；Precipitant solution and the uniform cocurrent of salting liquid are added drop-wise in three-necked flask, and quick stirring, control water-bath temperature
60 DEG C of degree, pH value adjust to 8, stir 12 hours, stand overnight.
[activation of catalyst]：By the solution after standing overnight, filtration washing is carried out, filter cake is then placed into water heating kettle and entered
Water-filling is heat-treated, 180 DEG C of hydro-thermal process temperature, 24 hours processing times.Then filtration washing is carried out again, will be deposited in 120
DEG C vacuum drying 12 hours, 800 DEG C be calcined 5 hours.
[evaluating catalyst]：Catalyst is loaded into fixed bed reactors, the composition of admixture of gas is CO2=333ml/
min,H2=667ml/min beds operate under 600 DEG C and 0.5Mpa, after reaction, by refrigerated separation water outlet.Evaluation
It the results are shown in Table 1.
Table 1*
* catalyst composition is molfraction in table.
[comparative example 1]
The preparation of carrier：A-take 200.0 grams of boehmite, 3.0 grams of pore creating material methylcellulose；40 grams of B-water intaking,
26 grams of zinc nitrate is added, adds 10.0 grams of the aqueous solution containing nitric acid 30% by weight percentage, mixed dissolution is uniform.By B
It is slowly added into A and stirs, after mediating 40 minutes, 100 DEG C of drying 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtains
To the complex carrier of shaping.
Vehicle element：Above-mentioned carrier is taken to dry activation 4 hours in 170 DEG C, it is standby.
Maceration extract is prepared：Weigh 42.9 grams of pin acid zirconium, 26.1 grams of barium nitrate, 50% 3.6 grams of manganese nitrate solution.Adding citric acid
7.6 grams, add water and dissolve by heating, be stirred to and be completely dissolved, weigh 100.0 grams of complex carriers, maceration extract is uniformly sprayed to load
On body, catalyst is both obtained after drying and roasting.
Catalyst is loaded into fixed bed reactors, the composition of admixture of gas is CO2=333ml/min, H2=667ml/
Min beds operate under 600 DEG C and 0.5Mpa, after reaction, by refrigerated separation water outlet.Evaluation result is shown in Table 2.
[comparative example 2]
The preparation of carrier：A-take 200.0 grams of boehmite, 3.0 grams of pore creating material methylcellulose；40 grams of B-water intaking,
26 grams of zinc nitrate is added, adds 10.0 grams of the aqueous solution containing nitric acid 30% by weight percentage, mixed dissolution is uniform.By B
It is slowly added into A and stirs, after mediating 40 minutes, 100 DEG C of drying 18 hours after extruded moulding, 800 DEG C of roastings 5 hours, obtains
To the complex carrier of shaping.
Vehicle element：Above-mentioned carrier is taken to dry activation 4 hours in 170 DEG C, it is standby.
Maceration extract is prepared：Claim 40.2 grams of titanium sulfate, 26.1 grams of barium nitrate, 20.5 grams of ferric nitrate, 50% manganese nitrate solution 18
Gram, add water and dissolve by heating, be stirred to and be completely dissolved, weigh 100.0 grams of complex carriers, maceration extract is uniformly sprayed at carrier
On, catalyst is both obtained after drying and roasting.
Catalyst is loaded into fixed bed reactors, the composition of admixture of gas is CO2=333ml/min, H2=667ml/
Min beds operate under 600 DEG C and 0.5Mpa, after reaction, by refrigerated separation water outlet.Evaluation result is shown in Table 2.
Table 2@
@Catalyst composition data is molfraction in table, and carrier is mass percent.
[embodiment 9~14]
The catalyst for taking selection example 5 to prepare, checks and rates catalyst, appraisal result is shown under different process operating condition
Table 3.
Table 3
Claims (10)
1. a kind of hydrogenation of carbon dioxide CO catalyst, in terms of molfraction, includes following components：
A) 0.9~10 part of metal Zr element and/or Ti elements；
B) 1~10 part of alkali earth metal；
C) 0.1~5 part of metal Fe element and/or Mn elements.
2. hydrogenation of carbon dioxide CO catalyst according to claim 1, it is characterised in that with molfraction
Meter, Zr and/or Ti content are 1~5 part.
3. hydrogenation of carbon dioxide CO catalyst according to claim 1, it is characterised in that Zr and Ti mole
Than (10：1)~(1：5).
4. hydrogenation of carbon dioxide CO catalyst according to claim 3, it is characterised in that Zr and Ti mole
Than (5：1)~(1：2).
5. hydrogenation of carbon dioxide CO catalyst according to claim 1, it is characterised in that with molfraction
Meter, the content of alkaline-earth metal is 1~5 part.
6. hydrogenation of carbon dioxide CO catalyst according to claim 1, it is characterised in that with molfraction
Meter, metal Fe and/or Mn content are 0.1~1 part.
7. hydrogenation of carbon dioxide CO catalyst according to claim 1, it is characterised in that selected from alkaline-earth metal
Element at least one of for Mg, Ca and Ba.
8. the preparation method of the hydrogenation of carbon dioxide CO catalyst described in any one of claim 1~7, including it is following
Step：
(i) the precursor salt solution A of Zr elements and/or Ti elements is prepared；
(ii) the precursor salt solution B selected from a kind of alkali earth metal is prepared；
(iii) the precursor salt solution C of Fe elements and/or Mn elements is prepared；
(iv) A, B, C are mixed, uniform stirring, is added drop-wise to precipitating reagent cocurrent in container and quick stirring, bath temperature control
At 60~80 DEG C, pH value is controlled 8~9；
(v) mother liquor is isolated, will be dried after precipitation progress hydro-thermal process, roasting obtains finished product.
A kind of 9. method of hydrogenation of carbon dioxide carbon monoxide, using carbon dioxide and hydrogen as unstripped gas, in reaction temperature 550
~600 DEG C, reaction pressure is normal pressure~1MPa, H2/CO2Volume ratio (1:1)~(3:And 6000~15000h of volume space velocity 1)-1Under the conditions of, unstripped gas obtains carbon monoxide and vapor with the catalyst haptoreaction described in any one of claim 1~7.
10. the method for hydrogenation of carbon dioxide carbon monoxide according to claim 9, the carbon monoxide of generation and water are steamed
Gas and the complete unstripped gas of unreacted separate water outlet, obtained containing carbon monoxide, titanium dioxide through subcooler, gas-liquid separator
The admixture of gas of carbon and hydrogen.
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