CN102600849B - Methanol cracking catalyst for methanol-gasoline dual-fuel automobiles and preparation and application thereof - Google Patents
Methanol cracking catalyst for methanol-gasoline dual-fuel automobiles and preparation and application thereof Download PDFInfo
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- CN102600849B CN102600849B CN201210058215.XA CN201210058215A CN102600849B CN 102600849 B CN102600849 B CN 102600849B CN 201210058215 A CN201210058215 A CN 201210058215A CN 102600849 B CN102600849 B CN 102600849B
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Abstract
A methanol cracking catalyst for methanol-gasoline dual-fuel automobiles comprises, by mass percentage, 7.5%-15.5% of NiO (nickel oxide), 2.0%-6.0% of additive, 78.5%-90.5% of complex carrier, wherein the additive can be two of CuO (cupric oxide), ZnO (zinc oxide), K2O (potassium oxide) or CaO(calcium oxide), and the complex carrier comprises, by weight, 30.0%-80.0% of SiO2 and 20.0%-70.0% of Al2O3. Since the complex of SiO2 and Al2O3 is used as a carrier, nitrate aqueous solution of Ni and the additive serves as impregnation solution, nitrate aqueous solution of active components and the additive are impregnated to the complex carrier by the equal-volume method, and finally the finished catalyst is obtained by drying the complex carrier and the calcining the same for 3-5 hours at the temperature ranging from 500 DEG C to 600 DEG C under air or nitrogen gas atmosphere. The methanol cracking catalyst has the advantages of high activity and fine selectivity and stability.
Description
Technical field
The invention belongs to catalysis methanol cracking field, be specifically related to one for Methanol-gasoline dual-fuel automobile system, catalysis methanol is with the Catalysts and its preparation method of car cracking hydrogen production.
Background technology
Enter after 21 century, the energy and environment become the major issue that human society faces, in recent years, the sharply increase of automobile quantity has aggravated these problems especially, because the pollution that vehicle exhaust brings accounts for 42% of whole atmosphere pollution, for automobile problem, each state is all in the new technology of making great efforts exploitation reduction auto-pollution, if mixed power electric car (HEV), pure electric automobile (BEV), FC-EV (FCEV) and methyl alcohol are with new-energy automobile of car hydrogen manufacturing etc., wherein methyl alcohol has larger competitive advantage with car hydrogen producing technology.
Methyl alcohol refers to and utilizes using waste heat from tail gas with car hydrogen producing technology, and methyl alcohol is cracked into hydrogen-rich gas under the effect of catalyst, is then mixed into engine combustion with gasoline, after methanol conversion is hydrogen-rich gas, calorific value increases, and efficiency of combustion improves, and this new technology shows obviously energy-conservation, emission reduction effect.Adopt the road examination result of the test of this technology to show, with methyl alcohol Substitute For Partial gasoline, can keep dynamic property at least not reduce under prerequisite, reach effect more than fuel-economizing 15%-25%.Testing result shows, adds tail gas CO and HC discharge minimizing 90%, NOx minimizing 40% after alcohol hydrogen.
Methyl alcohol is catalyst with the core of car hydrogen manufacturing, and it has higher requirement to catalyst: 1. the waste heat supply temperature of vehicle exhaust is higher, and unstable, and therefore catalyst needs high temperature resistant and temperature fluctuation; 2. stable product distributes, and is conducive to the steady running of engine; 3. automobile in the process of moving, shakes greatlyr, and therefore catalyst should have higher intensity.According to this, require knownly, the equal difficulty of existing industrializeding catalyst meets vehicle-mounted requirement.
Both domestic and external studies show that, methanol cracking catalyst comprises noble metal system and base metal system, wherein noble metal system has good catalytic activity and high-temperature stability, but greatly restricted because cost is high.In base metal system, with copper-based catalysts most study, but copper-based catalysts heat resistance is poor, and easy-sintering inactivation, is difficult to meet the demands, and Comparatively speaking, nickel-base catalyst has good high-temperature behavior, but product difference under high temperature and low temperature is larger.Existing catalyst all needs prereduction processing before use, not easy to operate on onboard system, and in addition, catalyst mechanical strength is inadequate, and easily efflorescence, causes the obstruction of gas circuit.
Summary of the invention
The object of the invention is for the deficiency of existing catalyst and a kind of methanol cracking catalyst that is applicable to Methanol-gasoline dual-fuel automobile and its preparation method and application is provided, catalyst is before use without hydrogen prereduction processing, methanol decomposition is had to good activity, selective and stability, and high temperature resistant and temperature fluctuation.
For achieving the above object, this catalyst quality fraction set becomes:
NiO=7.5%-15.5%, auxiliary agent=2.0%-6.0%, complexes carrier=78.5%-90.5%
Auxiliary agent is CuO, ZnO, K
2in O or CaO two kinds.
Complexes carrier mass fraction consists of: SiO
2=30.0%-80.0%, Al
2o
3=20.0%-70.0%;
Method for preparing catalyst of the present invention is as follows:
With SiO
2-Al
2o
3compound is as carrier, the nitrate aqueous solution of Ni and auxiliary agent is maceration extract, according to catalyst formulation, the nitrate solution of active component and auxiliary agent is flooded to complexes carrier by equi-volume process, after drying, under air or nitrogen atmosphere, 500 ℃-600 ℃, after roasting 3-5h, obtain finished catalyst.
Gained catalyst, without hydrogen prereduction processing, can be directly used in catalysis methanol cracking reaction.The process conditions of reaction are 320 ℃-550 ℃, mass space velocity 0.1-2.5h
-1, 0.01-0.2MPa.
Reaction condition as above is preferably 350 ℃-450 ℃, mass space velocity 0.1-2.0h
-1, 0.01-0.1MPa;
The method of testing of catalyst of the present invention is as follows: test is carried out on the fixed bed of continuous-flow, catalyst loading amount is 3.0ml, after filling, directly be warming up to reaction temperature, after temperature reaches, by SZB-2 double plunger micro pump, carry methyl alcohol, raw material is industrial methanol, after preheating, enters in reactor and reacts.Reaction is carried out getting gas phase and liquid product analysis after 20-24h, and product adopts two gas-chromatographies of being furnished with respectively Porapak T post, TDX-01 post and thermal conductivity cell detector to analyze, and obtains conversion ratio and selective.
Catalyst of the present invention has following features:
1, catalyst has good mechanical strength;
2, catalyst, without hydrogen prereduction processing, can directly apply to catalysis methanol cracking reaction;
3, high temperature and temperature fluctuation are little to the performance impact of catalyst.
Accompanying drawing explanation
Fig. 1 is the change curve of methanol conversion of the present invention with the reaction time.
The specific embodiment
The present invention is further illustrated for the following examples.
Embodiment 1
Take Ni (NO
3)
26H
2o 30.37g, Cu (NO
3)
23H
2o 4.86g, Ca (NO
3)
24H
2o 4.21g, adds water and is mixed with solution, and (composition mass fraction is: SiO by equi-volume impregnating, to be loaded to complexes carrier
2=50.0%, Al
2o
3=50.0%) upper, after drying, under air atmosphere, 600 ℃ of roasting 4h, obtain catalyst, and it consists of (mass fraction): NiO 7.80%, CuO 1.60%, CaO 1.00%, complexes carrier 89.60%.Gained catalyst packs into after reactor, is warming up to 350 ℃, at mass space velocity 0.25h
-1, react under 0.01MPa, methanol conversion is 86.3%, in product molar distribution, hydrogen accounts for 62.5%.Keep pressure constant, 380 ℃ of rising temperature values, at mass space velocity 1.05h
-1under condition, methanol conversion is 82.6%, and in product molar distribution, hydrogen accounts for 64.2%.
Embodiment 2
Take Ni (NO
3)
26H
2o59.18g, Cu (NO
3)
23H
2o 10.63g, KNO
34.29g, adds water and is mixed with solution, and preparation process is with embodiment 1, and wherein complexes carrier consists of: SiO
2=40.0%, Al
2o
3=60.0%, gained catalyst consists of (mass fraction): NiO 15.20%, CuO 3.50%, K
2o 2.00%, complexes carrier 79.30%.Evaluation method is with embodiment 1, at 400 ℃, mass space velocity 1.35h
-1, react under 0.1MPa, methanol conversion is 90.2%, in product molar distribution, hydrogen accounts for 62.3%.
Embodiment 3
Take Ni (NO
3)
26H
2o 36.99g, Zn (NO
3)
26H
2o 10.23g, Ca (NO
3)
24H
2o 5.05g, is mixed with the aqueous solution, and (composition mass fraction is: SiO to adopt equi-volume impregnating to be loaded to complexes carrier
2=70.0%, Al
2o
3=30.0%) upper, after drying, under nitrogen atmosphere, 500 ℃ of roasting 5h, obtain catalyst and consist of (mass fraction): NiO 9.50%, ZnO 2.80%, CaO 1.20%, complexes carrier 86.50%.Evaluating catalyst method is with embodiment 1, at 450 ℃, mass space velocity 1.95h
-1, react under 0.01MPa, methanol conversion is 90.2%, in product molar distribution, hydrogen accounts for 60.3%.
Embodiment 4
Take Ni (NO
3)
26H
2o 40.49g, Zn (NO
3)
26H
2o 12.43g, KNO
34.72g, is mixed with the aqueous solution, and (composition mass fraction is: SiO by equi-volume impregnating, to be loaded to complexes carrier
2=80.0%, Al
2o
3=20.0%) upper, after drying, under nitrogen atmosphere, 550 ℃ of roasting 3h, obtain catalyst and consist of (mass fraction): NiO 10.40%, ZnO 3.40%, K
2o 2.20%, complexes carrier 84.00%.Evaluating catalyst method is with embodiment 1, at 420 ℃, mass space velocity 1.05h
-1, react under 0.05MPa, methanol conversion is 88.5%, in product molar distribution, hydrogen accounts for 58.5%.
Embodiment 5
Embodiment 1-embodiment 4 gained catalyst are carried out to strength test, and the intensity that records catalyst is followed successively by 105N/ grain, 110N/ grain, 108N/ grain, 112N/ grain, and visible, the catalyst strength of exploitation is all greater than 100N/ grain.
Embodiment 6
Catalyst is with embodiment 3, at 380 ℃, mass space velocity 1.52h
-1, under 0.01MPa condition, catalyst continuous operation 244h the results are shown in Figure 1, as seen from the figure, in the reaction time, methanol conversion remains on more than 75%.After catalyst continuous operation 244h, keep other conditions constant, investigate the impact of temperature fluctuation, fluctuation program is: 380 ℃ is starting point, with 10 ℃/min, is warming up to 450 ℃, temperature is to rear maintenance 30min, then with 20 ℃/min, be down to 380 ℃, keep 60min, with this program repeat circulation, 24h analyzes once left and right, and analysis site fixes on 380 ℃ of constant temperature 60min stage random time points.The results are shown in Figure 1 last three some data, as seen from the figure, in 72.34h, conversion ratio changes less, visible, and the fluctuation of temperature is less to the activity influence of catalyst.
Claims (3)
1. for a methanol cracking catalyst for Methanol-gasoline dual-fuel automobile, it is characterized in that catalyst quality fraction set becomes: NiO=7.5%-15.5%, auxiliary agent=2.0%-6.0%, complexes carrier=78.5%-90.5%;
Auxiliary agent is CuO, ZnO, K
2in O or CaO two kinds;
Complexes carrier mass fraction consists of: SiO
2=30.0%-80.0%, Al
2o
3=20.0%-70.0%;
And prepare by the following method:
With SiO
2-Al
2o
3compound is as carrier, the nitrate aqueous solution of Ni and auxiliary agent is maceration extract, according to catalyst formulation, the nitrate solution of active component and auxiliary agent is flooded to complexes carrier by equi-volume process, after drying, under air or nitrogen atmosphere, 500 ℃-600 ℃, after roasting 3-5h, obtain finished catalyst.
2. the application of a kind of methanol cracking catalyst for Methanol-gasoline dual-fuel automobile as claimed in claim 1, it is characterized in that catalyst is without hydrogen prereduction processing, be directly used in catalysis methanol cracking reaction, the process conditions of reaction are 320 ℃-550 ℃, mass space velocity 0.1-2.5h
-1, 0.01-0.2MPa.
3. the application of a kind of methanol cracking catalyst for Methanol-gasoline dual-fuel automobile as claimed in claim 2, is characterized in that described reaction condition is 350 ℃-450 ℃, mass space velocity 0.1-2.0h
-1, 0.01-0.1MPa.
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