CN102626652B - Molecular sieve catalyst for purifying methane in tail gas of natural gas vehicles, preparation and application thereof - Google Patents
Molecular sieve catalyst for purifying methane in tail gas of natural gas vehicles, preparation and application thereof Download PDFInfo
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- CN102626652B CN102626652B CN201210078645.8A CN201210078645A CN102626652B CN 102626652 B CN102626652 B CN 102626652B CN 201210078645 A CN201210078645 A CN 201210078645A CN 102626652 B CN102626652 B CN 102626652B
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Abstract
The invention provides a molecular sieve catalyst for purifying methane in tail gas of natural gas vehicles. The catalyst takes transition metal elements cobalt and chromium as active components, which are loaded on a natural or synthetic molecular sieve. The total loading amount (by weight) of cobalt and chromium on the molecular sieve is 1-40%, and cobalt and chromium are in a mole ratio of 0.01-100. The preparation method of the molecular sieve catalyst consists of: dissolving the soluble salts of each component in deionized water in proportion so as to prepare a solution, then dispersing a carrier into the solution by means of ultrasound-assisted oscillation, conducting heating and drying, then carrying out roasting, thus obtaining the catalyst. When used in catalytic purification of methane in tail gas of natural gas vehicles, the catalyst of the invention has outstanding ability in oxidizing residual methane in tail gas of natural gas vehicles, and good water vapor and sulfur poisoning resisting abilities, as well as strong adaptability to severe environments. Meanwhile, the catalyst prepared in the invention has rich raw materials and low cost, thus boasting application prospects.
Description
Technical field
The invention belongs to environment-friendly engineering technical field, relate to the processing of vehicle exhaust, the molecular sieve catalyst and preparation and the application that particularly for natural gas vehicle tail gas methane, purify.
Background technology
The demand of environment and energy security aspect is just promoting gas combustion automobile (NGVs) and is worldwide developing rapidly.Data according to international gas combustion automobile association show, calendar year 2001 so far in world wide combustion gas automobile pollution average growth rate per annum reach 24%, and be expected to reach 6,500 ten thousand to the year two thousand twenty.Within 2010, China's 16 cleaning vehicle emphasis Model Cities (area) gas-fueled vehicles (CNG and LNG) recoverable amount is over 600,000.
Compare with diesel vehicle with gasoline car, gas-fueled vehicles have economic advantages, and have the good energy and environmental benefit.Yet along with Abgasgesetz is increasingly strict, catalytic cleaner is still the indispensable device of natural gas vehicle tail gas qualified discharge.In the HC of natural gas vehicle exhaust emissions, the overwhelming majority is methane (90～95%), and methane is the most difficult oxidized hydro carbons, and therefore, natural gas vehicle tai-gas clean-up catalyst must have higher transformation efficiency to methane.
At present, the main active of catalytic cleaner is the noble metals such as Pt, Pd and Rh, and noble metal is that Pd wherein will be far above other metallic catalysts to the clean-up effect of methane especially.Yet because noble metal is expensive, resource-constrained, has greatly restricted cost and the large-scale application of catalyst.Therefore, reduce the consumption of noble metal, even develop non-precious metal catalyst is study hotspot both domestic and external always.
It is generally acknowledged, the transition metals such as Co, Cr, Mn, Cu, Ni all have higher methane oxidation ability, all can think the active component of potential methane oxidation.Substrates has considerable influence to the performance of catalyst, and some researchers attempt utilizing molecular sieve supported transition metal component to prepare methane oxidation catalyst.(Russ.Chem.Bull., 2003,52,1933 such as K.I.Slovetskaya; Russ. Chem.Bull., 2004,53,2168) studied and take the Co-ZSM-5 integral catalyzer that Fe-Cr-Al alloy is carrier, for the reaction of methane high-temperature oxydation, and investigated its stability under reaction condition.E.Asedegbega-Nieto etc. (Catal.Today, 2011,157,425) have reported the LTA molecular sieve catalyst of cobalt ions exchange, and this catalyst has similar Catalytic methane oxidation active to Co3O4.The people such as K.S.Hui have prepared the 13X molecular sieve catalyst that comprises four kinds of transition metal (Cu, Cr, Ni and Co) ion-exchange by ion-exchange, and this catalyst is purified to (Combust.Flame for natural gas vehicle (NGVs) tail gas methane, 2008,153,119).
CN101549301 has prepared a kind of natural gas vehicle tail gas clean-up integral catalyzer, and this catalyst relates to the molecular sieve by metal oxide modified.The metal oxide that described modified molecular screen adopts is MgO, BaO, SrO, La
2o
3, CeO
2, Y
2o
3, Nd
2o
3, ZrO
2, NiO, CuO, Fe
2o
3, ZnO, TiO
2in one or more; Described molecular sieve comprises: ferrierite, ZSM-5, beta molecular sieve, Y zeolite, modenite, SAPO molecular sieve or their mixture.The claim of noticing this patent comprises 13 kinds of alkaline-earth metal or transition metal, but does not relate to Elements C o and Cr.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of molecular sieve catalyst and preparation and application purifying for natural gas vehicle tail gas methane, it can be used for the catalytic purification of natural gas and auto tail gas methane, and has higher stability.
To achieve these goals, the technical solution used in the present invention is:
A kind of molecular sieve catalyst purifying for natural gas vehicle tail gas methane, using transition metal cobalt and chromium as active component, be supported on natural or artificial synthetic molecular sieve, described molecular sieve is beta molecular sieve, ZSM-5 molecular sieve, ferrierite, modenite, Y zeolite or SAPO molecular sieve, on molecular sieve, total loading (by weight) of cobalt and chromium is 1～40%, and cobalt chromium mol ratio is between 0.01～100.
The cobalt supporting on described molecular sieve and the mol ratio of chromium are 1: 2 o'clock, and catalytic activity is optimum.
The present invention also provides a kind of preparation method of described molecular sieve catalyst, comprises the following steps successively:
Step 1, is raised to 350 ± 20 ℃ with the heating rate of 1 ℃/min from room temperature by molecular screen material, keeps 1～2 hour; Continuation is warming up to 550～600 ℃ with the heating rate of 1 ℃/min, and keeps 8～12 hours;
Molecular sieve can be removed template after high-temperature roasting, and can destroy some anionic groups, forms the form of complicated multi-component metal oxide; For the lower process of synthesis temperature, can introducing portion pore structure in roasting process, and be accompanied by crystallization to a certain degree.
Step 2, is dissolved in the solubility cobalt salt of aequum and solubility chromic salts in deionized water in proportion, wiring solution-forming, and solution concentration is 1～2mol/L, as the precursor solution of Kaolinite Preparation of Catalyst;
Wherein said solubility cobalt salt is: cobalt nitrate, and cobalt acetate, cobalt chloride etc., solubility chromic salts is chromic nitrate, chromium chloride etc.; When above-mentioned soluble metallic salt is nitrate, effect is better.
Step 3, adopts co-impregnation, and gained molecular sieve in step 1 is immersed in the precursor solution that contains active component in step 2, and the weight ratio of molecular sieve and solution is between 1: 10～1: 2000; Adopt mechanical agitation or magnetic agitation fully to stir 1～4 hour, mixed liquor is processed to 1～10h by the mode of ultrasonic wave auxiliary oscillating, obtain mixture solution;
The present invention utilizes the mode of ultrasonic wave auxiliary oscillating that carrier height is scattered in the aqueous solution; The frequency range of supersonic oscillations is 15～100kHz; Mechanical agitation or magnetic agitation speed are 200～600rpm; Supersonic oscillations can make molecular sieve dispersed, and hyperacoustic pyrogenic action also can evaporation section moisture.
Step 4 under uniform stirring, heats gained mixture solution 1～12 hour in 60～80 ℃ of temperature ranges, and then 100～120 ℃ are dried 4～24 hours;
Step 5,500～700 ℃ of roastings 2～6 hours, obtains catalyst prod by step 4 products therefrom.
The application of molecular sieve catalyst of the present invention in natural gas vehicle tail gas methane purifies, reaction condition is: O in reaction gas
2/ CH
4volumetric concentration ratio is 5～100, and applicable air speed is at 5000h
-1to 100,000h
-1between, reaction pressure is normal pressure, applicable operating temperature is 250～600 ℃.
Compared with prior art, molecular sieve catalyst of the present invention is outstanding to the remaining methane oxidation ability of natural gas and auto tail gas, and water resistant steam, sulfur poisoning-resistant ability are better, have the adaptable advantage of adverse circumstances.Meanwhile, the catalyst raw material being made by the present invention is abundant, with low cost, possesses application prospect.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment mono-
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 5% and 9% to be supported on that molecular sieve HBEA (H type beta-molecular sieve) is upper to be formed.
Its preparation method comprises the steps:
Step 1, is raised to 330 ℃ with the heating rate of 1 ℃/min from room temperature by molecular sieve HBEA, keeps 1 hour; Continuation is warming up to 550 ℃ with the heating rate of 1 ℃/min, and keeps 10 hours;
Step 2, is dissolved in required cobalt nitrate and chromic nitrate in deionized water in proportion, wiring solution-forming, and solution concentration is 1mol/L, as the precursor solution of Kaolinite Preparation of Catalyst;
Step 3, adopts co-impregnation, and gained molecular sieve in step 1 is immersed in the precursor solution that contains active component in step 2, and the weight ratio of molecular sieve and solution is 1: 100; Adopt magnetic agitation fully to stir 2 hours, mixed liquor is processed to 4h by the mode of ultrasonic wave auxiliary oscillating, obtain mixture solution;
Step 4, by gained mixture solution, under uniform stirring, 60 ℃ are heated 6 hours, and then 110 ℃ are dried 12 hours;
Step 5,600 ℃ of roastings 4 hours, obtains Co (5%)-Cr (9%)/HBEA catalyst prod by step 4 products therefrom.
Catalyst compressing tablet is sieved, choose 40～60 object particles standby.
Embodiment bis-
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 5% and 9% to be supported on that molecular sieve ZSM-5 is upper to be formed.
Its preparation method comprises the steps:
Step 1, is raised to 350 ℃ with the heating rate of 1 ℃/min from room temperature by molecular sieve ZSM-5, keeps 2 hours; Continuation is warming up to 600 ℃ with the heating rate of 1 ℃/min, and keeps 8 hours;
Step 2, is dissolved in the solubility cobalt salt of aequum and solubility chromic salts in deionized water in proportion, wiring solution-forming, and solution concentration is 2mol/L, as the precursor solution of Kaolinite Preparation of Catalyst;
Step 3, adopts co-impregnation, and gained molecular sieve in step 1 is immersed in the precursor solution that contains active component in step 2, and the weight ratio of molecular sieve and solution is 1: 2000; Adopt magnetic agitation fully to stir 1 hour, mixed liquor is processed to 1h by the mode of ultrasonic wave auxiliary oscillating, obtain mixture solution;
Step 4, by gained mixture solution, under uniform stirring, 80 ℃ of heating 4 hours, then 100 ℃ were dried 5 hours;
Step 5,700 ℃ of roastings 6 hours, obtains Co (5%)-Cr (9%)/ZSM-5 catalyst prod by step 4 products therefrom.
Embodiment tri-
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 5% and 9% to be supported on that molecular sieve FER is upper to be formed.
Its preparation method comprises the steps:
Step 1, is raised to 370 ℃ with the heating rate of 1 ℃/min from room temperature by molecular sieve FER, keeps 1 hour; Continuation is warming up to 550 ℃ with the heating rate of 1 ℃/min, and keeps 12 hours;
Step 2, is dissolved in the solubility cobalt salt of aequum and solubility chromic salts in deionized water in proportion, wiring solution-forming, and solution concentration is 2mol/L, as the precursor solution of Kaolinite Preparation of Catalyst;
Step 3, adopts co-impregnation, and gained molecular sieve in step 1 is immersed in the precursor solution that contains active component in step 2, and the weight ratio of molecular sieve and solution is 1: 10; Adopt mechanical agitation fully to stir 2 hours, mixed liquor is processed to 8h by the mode of ultrasonic wave auxiliary oscillating, obtain mixture solution;
Step 4 under uniform stirring, heats gained mixture solution 10 hours in 70 ℃ of temperature ranges, and then 120 ℃ are dried 4 hours;
Step 5,500 ℃ of roastings 2 hours, obtains Co (5%)-Cr (9%)/FER catalyst prod by step 4 products therefrom.
Embodiment tetra-
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 5% and 9% to be supported on that molecular sieve MOR is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (5%)-Cr (9%)/MOR catalyst prod.
Embodiment five
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 5% and 9% to be supported on that molecular sieve HY is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (5%)-Cr (9%)/HY catalyst prod.
Embodiment six
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 5% and 9% to be supported on that molecular sieve SAPO is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (5%)-Cr (9%)/SAPO catalyst prod.
Embodiment seven
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 0.5% and 0.5% to be supported on that molecular sieve SAPO is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (0.5%)-Cr (0.5%)/SAPO catalyst prod.
Embodiment eight
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 0.1% and 10% to be supported on that molecular sieve SAPO is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (0.1%)-Cr (10%)/SAPO catalyst prod.
Embodiment nine
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 38% and 2% to be supported on that molecular sieve HY is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (38%)-Cr (2%)/HY catalyst prod.
Embodiment ten
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 10% and 20% to be supported on that molecular sieve FER is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (10%)-Cr (20%)/FER catalyst prod.
Embodiment 11
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 10% and 0.1% to be supported on that molecular sieve MOR is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (10%)-Cr (0.1%)/MOR catalyst prod.
Embodiment 12
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 2.5% and 4.5% to be supported on that molecular sieve HBEA is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (2.5%)-Cr (4.5%)/HBEA catalyst prod.
Embodiment 13
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 10% and 18% to be supported on that molecular sieve HBEA is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (10%)-Cr (18%)/HBEA catalyst prod.
Embodiment 14
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take the Cr of Co that weight percentage is 2.5% and 11.5% to be supported on that molecular sieve HBEA is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (2.5%)-Cr (11.5%)/HBEA catalyst prod.
Catalyst of the present invention is carried out under excess oxygen to methane oxidation active testing, active testing carries out in fixed bed reactors.Before entering reactor, methane, oxygen and nitrogen fully mix in blender.Gas composition in catalyst activity evaluation experimental (volume fraction) is: CH
40.5%, O
210%; N
2for molecular balance gas, the total flow of gas is 150mL/min, and corresponding reaction velocity (GHSV) is 40,000h
-1; Reaction pressure is normal pressure; Reactor is as in a temperature control electric furnace, and reaction temperature is 250～600 ℃.By online chromatography analysis product, catalyst activity represents with methane conversion (%).
For ease of comparing effect of the present invention, set comparative example as follows:
Comparative example 1:Co (5%)/HBEA
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take Co that weight percentage is 5% to be supported on that molecular sieve HBEA is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Co (5%)/HBEA catalyst prod.
Comparative example 2:Cr (9%)/HBEA
The molecular sieve catalyst purifying for natural gas vehicle tail gas methane is to take Cr that weight percentage is 9% to be supported on that molecular sieve HBEA is upper to be formed.
Its preparation method is consistent with embodiment mono-, makes Cr (9%)/HBEA catalyst prod.
Test result analysis comparison
HBEA molecular sieve catalyst take below as example, total loading is described, the impact of different cobalt chromium mol ratios on Catalytic methane oxidation ability.Table one has been listed comparative example one, two, and the catalytic activity test result of the prepared catalyst of embodiment mono-, 12,13 and 14 under above-mentioned active testing condition, and this catalyst series has good methane low-temperature oxidation activity as seen; The activity that supports Co and the bimetallic catalyst of Cr is obviously better than supporting monometallic molecular sieve catalyst; And total loading of Co and Cr and different cobalt chromium mol ratio have certain influence to catalytic activity.
Methane conversion comparison on table 1HBEA molecular sieve catalyst
Reaction condition: CH
40.5%, O
210%, N
2for molecular balance gas, air speed is 40,000h
-1, reaction pressure is normal pressure.
Claims (3)
1. the preparation method of the molecular sieve catalyst purifying for natural gas vehicle tail gas methane, described molecular sieve is usingd transition metal cobalt and chromium as active component, be supported on natural or artificial synthetic molecular sieve, described molecular sieve is beta molecular sieve, ZSM-5 molecular sieve, ferrierite, modenite, Y zeolite or SAPO molecular sieve, on molecular sieve, total loading (by weight) of cobalt and chromium is 1～40%, and cobalt chromium mol ratio is between 0.01～100;
It is characterized in that, comprise the following steps successively:
Step 1, is raised to 350 ± 20 ℃ with the heating rate of 1 ℃/min from room temperature by molecular screen material, keeps 1～2 hour; Continuation is warming up to 550～600 ℃ with the heating rate of 1 ℃/min, and keeps 8～12 hours;
Step 2, is dissolved in the solubility cobalt salt of aequum and solubility chromic salts in deionized water in proportion, wiring solution-forming, and solution concentration is 1～2mol/L, as the precursor solution of Kaolinite Preparation of Catalyst;
Step 3, adopts co-impregnation, and gained molecular sieve in step 1 is immersed in the precursor solution that contains active component in step 2, and the weight ratio of molecular sieve and solution is between 1:10～1:2000; Adopt mechanical agitation or magnetic agitation fully to stir 1～4 hour, mixed liquor is processed to 1～10h by the mode of ultrasonic wave auxiliary oscillating, obtain mixture solution;
Step 4 under uniform stirring, heats gained mixture solution 1～12 hour in 60～80 ℃ of temperature ranges, and then 100～120 ℃ are dried 4～24 hours;
Step 5,500～700 ℃ of roastings 2～6 hours, obtains catalyst prod by step 4 products therefrom.
2. the preparation method of the molecular sieve catalyst purifying for natural gas vehicle tail gas methane according to claim 1, is characterized in that, in described step 2, solubility cobalt salt is cobalt nitrate, cobalt acetate or cobalt chloride, and solubility chromic salts is chromic nitrate or chromium chloride.
3. the preparation method of the molecular sieve catalyst purifying for natural gas vehicle tail gas methane according to claim 1, is characterized in that, in described step 3, mechanical agitation or magnetic agitation speed are 200～600rpm.
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| CN110773120B (en) * | 2019-11-08 | 2021-05-07 | 四川大学 | Metal salt modified molecular sieve and preparation method and application thereof |
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Non-Patent Citations (2)
| Title |
|---|
| Catalytic combustion of methane over cerium-doped cobalt chromite catalysts;Jinghuan Chen et al.;《Catalysis Today》;20110502;第175卷;216-222 * |
| Jinghuan Chen et al..Catalytic combustion of methane over cerium-doped cobalt chromite catalysts.《Catalysis Today》.2011,第175卷 |
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