CN109701614A - A kind of preparation method of hud typed Beta molecular sieve catalyst - Google Patents
A kind of preparation method of hud typed Beta molecular sieve catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of hud typed Beta molecular sieve catalyst, belong to zeolite molecular sieve synthetic technology field, more particularly to one kind with the zeolite-loaded noble metal of internal layer Beta, the core-shell type molecular sieve catalyst of external sheath richness aluminium Beta zeolite, the fragrant ethers compound for catalysis hydrogenation deoxidation that may be used as in lignin derivative generate unsaturated aromatic hydrocarbon liquid fuel.Principal product cyclohexane selectivity reaches 98% or more, and conversion ratio is close to 90%.This method reaction condition is mild, and active, selective and good stability with higher is suitable for industrial production.
Description
Technical field
The invention belongs to zeolite molecular sieve synthetic technology fields, more particularly to one kind with your molecular sieve carried gold of internal layer
Belong to, the hud typed Beta zeolite catalyst of external sheath molecular sieve may be used as the fragrant ethers chemical combination in lignin derivative
Object catalytic hydrodeoxygenation generates unsaturated aromatic hydrocarbon liquid fuel.
Background technique
Energy problem is the critical issue of progress of human society and development.Since 21 century, demand day of the mankind to the energy
It is cumulative to add.It is limited as traditional non-renewable resources reserves of representative using petroleum, coal and natural gas, and deposit in use
The environmental pollutions such as greenhouse gas emission, acid rain the problem of.And in numerous renewable energy, biomass is that a kind of type is numerous
More and environmentally protective clean energy resourcies.But bio oil complicated composition, containing including ether, phenol, furans, ketone, aldehyde, alcohol, acid and ester etc.
A large amount of oxygenatedchemicals significantly reduces oil quality, and such as low heat value, chemical instability, viscosity is big and corrodes to equipment
Deng seriously hindering its being widely used as petrol and diesel oil alternative fuel.Hydrogenation deoxidation is considered as most having to biomass upgrading
The upgrading mode of effect.
Beta molecular sieve is a kind of with the silica-rich zeolite molecular sieve for intersecting twelve-ring channel design, belongs to BEA and opens up benefit
Structure.In its crystal structure along 100 and 010 direction be mutually perpendicular straight channel, aperture be 0.66 × 0.77nm；Along 001
Direction is through the Z-type bending duct of 100 and 010 direction straight channel, and aperture is 0.56 × 0.65nm.The unique three-dimensional apertures of Beta
Road system is conducive to the diffusion of reactant molecule and product molecule, is widely used to hydrocarbons hydrogenation cracking, hydroisomerization, alkane
The petrochemical industries catalytic fields such as hydrocarbon aromatizing, alkylation and alkene hydration.
Patent CN105498827A, which is reported, a kind of utilizes Beta zeolite molecular sieve for biomass-based furan derivatives system
The method of aromatic hydrocarbons, reaction temperature is high, and liquid products conversion rate is low.Conversion ratio is only 44% after reaction, product aromatics
Selectivity is 62%.105013527 B of patent CN discloses a kind of preparation method of core-shell structure Beta molecular sieve.Study people
Member has inside and outside two using supported copper/ferriferous oxide total silicon Beta zeolite as crystal seed under organic formwork agent guiding role
Layer Beta zeolite and metal oxide are wrapped in interior molecular sieve catalyst, to product hydrogen in ethanol steam reforming reaction
Gas shows highly selective.But the participation of organic formwork agent is needed in the synthesis process of hud typed material.Patent CN
102909065 B disclose a kind of synthetic method of Y-Beta composite molecular screen with core-shell structure, and this method uses first
Organic formwork agent carries out ion exchange to Y-type zeolite molecular sieve, plays structure directing to generate outer layer Beta molecular sieve in next step
Effect has obtained a kind of core-shell catalyst that outer layer is Beta, has improved carbon accumulation resisting ability and reaction selectivity, but the preparation
The method of core-shell catalyst, which still needs, uses a large amount of organic formwork agents.
In conclusion utilizing it the present invention is directed to develop a kind of high performance hud typed Beta zeolite molecular sieve catalyst
The concerted catalysis effect of unique core-shell structure and inner layer metal with catalytic activity, a step adds hydrogen de- in a mild condition
Oxygen realizes the highly selective method for generating saturated alkane liquid fuel.And Beta zeolite seed crystal is only utilized in synthetic method
Structure-directing effect generate the Beta zeolite molecular sieve of outer layer, sial acid group in crystal seed and gel is only strengthened by gel aging
The interaction of ion promotes nucleation and crystal growth, improves the quality of product, is a kind of environmental-friendly synthetic method.
Summary of the invention
The present invention provides a kind of noble metal active component core-shell catalyst evenly dispersed inside Beta molecular sieve,
Reacted evaluation confirms that this coreshell type structure substantially increases the selectivity of product hexamethylene.Not only efficiently utilize reserves
Biomass renewable resource abundant, and provide a kind of extensive system of unsaturated alkane fuel in non-traditional fossil energy
Standby new way, has a good application prospect.
Technical solution of the present invention:
A kind of preparation method of hud typed Beta molecular sieve catalyst, steps are as follows:
Step 1: using urea precipitation method or NaBH4Reduction method loads in Beta molecular sieve seed according to noble metal
The ratio of 0.5wt.%~2wt.% uniformly contacts noble metal precursor body with the Beta molecular sieve seed of addition in the solution；
The SiO of inner layer B eta molecular sieve2/Al2O3Molar ratio is 22.0~31.8, before the molecular sieve carried required noble metal of inner layer B eta
Driving body salt is chloroplatinic acid or palladium chloride；The SiO of outer layer Beta molecular sieve2/Al2O3Molar ratio is 9.8-13.0；
Step 2: collecting product, it is separated by solid-liquid separation, 450 DEG C of roasting 3h, obtaining that treated, Beta molecular sieve seed is
Pt-Beta；
Step 3: silicon source, sodium hydroxide are dissolved in respectively in deionized water after formation clear solution, the two is uniformly mixed
Afterwards, desired amount of silicon source is slowly added thereto, forms homogeneous gel；It, will under conditions of being not higher than 120 DEG C of crystallization temperatures
It seals ageing and stands 0~10 hour；
Silicon source in the raw material, silicon source, sodium hydroxide and deionized water original mole of composition are as follows: SiO2/Al2O3=
40~60, Na2O/SiO2=0.30~0.42, TEA+/SiO2=0~0.10, H2O/SiO2=20~35；
Step 4: being added to second step according to required amount through at aging by the Beta molecular sieve seed that processing obtains
It stirs evenly, then shifts mixed gel in stainless steel kettle, incubation water heating crystallization under the conditions of 120~140 DEG C in the gel of reason
36~120 hours；After crystallization, product is collected through separation of solid and liquid, washing, drying, obtains cladding noble metal nano particles
Hud typed Beta molecular sieve catalyst.
It is 6wt.%~12wt.% of the 4th step gross mass that second step, which obtains Pt-Beta as the additive amount of crystal seed,；It obtains
The best degree of crystallization of product and rationally addition crystal seed amount, preferably seed load are 10wt.%.
The silicon source is white carbon black, silica solution or ethyl orthosilicate；Silicon source is sodium metaaluminate or aluminium powder.
The Beta core-shell type molecular sieve catalyst that the present invention is prepared can be applied in lignin derivative aromatization
In the reaction for closing object.
Beneficial effects of the present invention: the Beta core-shell type molecular sieve that the present invention mentions is as fragrant ethers hydrogenation deoxidation reaction
Catalyst passes through the synergistic effect of the noble metal nano particles of the zeolite molecular sieve and load of inside and outside two layers difference acid strength, phase
Than the catalyst of uncoated outer layer Beta molecular sieve, which shows the high selectivity to principal product hexamethylene.
Detailed description of the invention
Fig. 1 is the XRD spectra of product Beta core-shell type molecular sieve catalyst of the present invention.
Fig. 2 is the TEM spectrogram of Beta core-shell type molecular sieve catalyst using 200nm as scale.
Fig. 3 is the TEM spectrogram of Beta core-shell type molecular sieve catalyst using 20nm as scale.
Specific embodiment
The present invention will be described in detail below by embodiment, but the invention is not limited to these embodiments.
Embodiment 1
The first step weighs 0.056g NaOH, 0.59g sodium metaaluminate (57wt.%Al2O3, 43wt.%Na2O) it is added to dress
There are 19g tetraethyl ammonium hydroxide solution (25wt.%TEAOH, 75wt.%H2O clear solution is mixed to form in three-necked flask).
Then with vigorous stirring slowly to mixed solution and dripping 15g silica solution (40wt.%SiO2, 60wt.%H2), O 0.5 is stirred
White mixture gel is formed after hour.Mixture gel obtained is transferred in the stainless steel kettle with polytetrafluoroethyllining lining
140 DEG C of hydro-thermal thermostatic crystallization 3 days, crystallization collect through cooling, centrifugation, washing, drying after completing and obtain white solid powder product.
Belong to the good little crystal grain Beta zeolite of crystallization degree through X-ray diffraction analysis measurement.The ingredient proportion of each material are as follows: 1SiO2:
0.033Al2O3:0.048Na2O:0.32TEAOH:12.64H2O.
The crystal seed of synthesis is placed into Muffle furnace by second step, and 550 DEG C roast 5 hours, is made inside Beta zeolite seed crystal
Combination water and template sufficiently remove.Open Muffle furnace after cooling, collect sample carry out being sized to 100 mesh hereinafter, with
The NH of 0.5mol/L4NO380 DEG C of constant temperature of solution carry out NH to sample4 +Exchange, solid-to-liquid ratio 30:1, exchange 1 hour, exchanges three every time
After secondary, 3.70g white powder H-Beta zeolite product is obtained through drying, 550 DEG C of roastings.
Third step is measured and is mixed in 10.84ml chloroplatinic acid (1.0g/100ml) solution and 100ml deionized water round-bottomed flask
It is formed uniformly yellow solution, 2.40g urea is added, adds magnetic stir bar to stir, dissolves solid sufficiently, then by 2.00g system
In standby H-Beta product addition system.Round-bottomed flask equipped with Beta crystal seed and mixed solution is transferred in oil bath pan and is flowed back
Heating is heated to 50 DEG C and is kept for 0.5 hour, then is warming up to 80 DEG C and maintains 0.5 hour, finally heats up 90 DEG C and obtains for constant temperature 24 hours
Milky white product.
4th step collects milky white product and is separated by solid-liquid separation, is washed, being dried to obtain white solid product, in two stages
Product of roasting: the first stage is 400 DEG C of air atmosphere and aoxidizes 4 hours that second stage uses 300 DEG C of hydrogen atmosphere reduction instead after cooling
3 hours.Collection obtains 1.85g Dark grey Pt-Beta solid product, is named as Pt-Beta crystal seed 1.
5th step is made into clear solution A with 24g deionized water dissolving 2.84g sodium hydrate solid；24g deionization is used again
Water dissolution 0.44g sodium metaaluminate solid is made into clear solution B.With vigorous stirring after mixing by the two, with 2.0ml/min
Speed be slowly added to 12.5ml silica solution, solution is placed in 60 DEG C of water-baths, stirring obtains white mixed gel in 1 hour.?
By mixed gel sealing and standing 3 hours at 130 DEG C, cooling is taken out rapidly, 0.66g Pt-Beta crystal seed is taken to be added to mixed gel
In, it is vigorously agitated again 5 minutes.After forming crystal seed-gel mixture, it is transferred into the stainless steel kettle with polytetrafluoroethyllining lining
In 130 DEG C incubation water heating crystallization 40 hours.The ingredient proportion of each material are as follows: 1SiO2:0.025Al2O3:0.387Na2O:27H2O,
Seed load is 10wt.%.
6th step, through cooling, centrifugation, washing, drying after crystallization completion, collection obtains 1.78g light grey solid particle.Through
Lower 350 DEG C of air atmosphere roast 3 hours, use 300 DEG C of reductase 12 hours of hydrogen atmosphere instead after cooling, obtain hud typed Pt@Beta
Molecular sieve catalyst sample 1.
Fig. 1 is the XRD spectra of crystal seed used in No. 1 sample and sample of the present embodiment.The core-shell catalyst of synthesis
With significant Beta characteristic diffraction peak, crystal structure is compared its characteristic diffraction peak intensity with crystal seed for Beta pure phase and is significantly become
By force, this phenomenon and the particle size and silica alumina ratio of core-shell type molecular sieve composition change related；It should through x-ray fluorescence analysis
The silica alumina ratio of catalyst is 11.2, illustrates that the surface of molecular sieve forms the molecular sieve shell of rich aluminium profiles.
Embodiment 2
The first step weighs 0.22g aluminium powder and is slowly added into the three-necked flask equipped with 39.9g tetraethyl ammonium hydroxide solution
It is vigorously stirred to clarification.The three-necked flask equipped with mixed solution is then put into 60 DEG C of heating water baths, 6.0g is added into solution
White carbon black (95.0wt.%SiO2, 5.0wt.%H2), O pale white mixture gel is formed after being vigorously stirred 1 hour.It will be made again
Mixed gel be transferred to 140 DEG C of hydro-thermal static crystallization 4 days in stainless steel kettle, crystallization complete after through cooling, centrifugation, washing, dry
Dry collection obtains white solid powder product.It is Beta zeolite through X-ray diffraction analysis measurement product, it is preferable belongs to crystallization
Beta zeolite product.The ingredient proportion of each material are as follows: 1SiO2: 0.04Al2O3:0.14Na2O:0.27TEAOH:14H2O。
Beta zeolite product is directly placed into Muffle furnace by second step, and 550 DEG C roast 5 hours, due to synthesis process
In sodium source is not added, therefore do not need NH4 +Exchange, directly obtains 3.25g H-Beta zeolite seed crystal after roasting.
Third step is measured and is mixed in 10.84ml chloroplatinic acid (1.0g/100ml) solution and 100ml deionized water round-bottomed flask
It is formed uniformly yellow solution, 2.40g urea is added, dissolves solid sufficiently, then the H-Beta product of 2.00g preparation is added
In system.It is heated to 50 DEG C to be kept for 0.5 hour, then is warming up to 80 DEG C and maintains 0.5 hour, it is small to be finally warming up to 100 DEG C of constant temperature 24
When obtain milky white product.
4th step collects Dark grey product and is separated by solid-liquid separation, is washed, being dried to obtain gray solid product, in two stages
Product of roasting: the first stage is 400 DEG C of air atmosphere and aoxidizes 4 hours that second stage uses 300 DEG C of hydrogen atmosphere reduction instead after cooling
3 hours.Collection obtains 0.75g Dark grey Pt-Beta solid product, is named as Pt-Beta crystal seed 2；
5th step is made into clear solution A with 24g deionized water dissolving 2.84g sodium hydrate solid；24g deionization is used again
Water dissolution 0.44g sodium metaaluminate solid is made into clear solution B.With vigorous stirring after mixing by the two, in 80 DEG C of water-baths
It is slowly added to 6.0g white carbon black, stirring obtains white mixed gel in 1 hour.0.66g Pt-Beta crystal seed is finally weighed to be added to
In mixed gel, it is vigorously agitated again 15 minutes.After forming crystal seed-gel mixture, by mixed gel sealing and standing at 100 DEG C
5 hours rapid cooling addition crystal seeds, subsequent 140 DEG C of incubation water heating crystallization 40 hours.The ingredient proportion of each material are as follows: 1SiO2:
0.025Al2O3:0.387Na2O::27H2O, seed load 10wt.%.
6th step, through cooling, centrifugation, washing, drying after crystallization completion, collection obtains 1.78g light grey solid particle.Through
Lower 350 DEG C of air atmosphere roast 3 hours, use 300 DEG C of reductase 12 hours of hydrogen atmosphere instead after cooling, obtain hud typed Pt@Beta
Molecular sieve catalyst sample 2.
Embodiment 3
The first, second step in embodiment 1 is repeated, is fired, NH4 +It is solid that white is obtained after exchange, washing, dry, roasting
Body powder Beta product.
Third step weighs 10.0mg polyvinylpyrrolidone (PVP, K30) and is added to the round bottom equipped with 50ml deionized water
In flask, 2.14ml chlorine palladium acid solution (1.0g/100ml) is added dropwise after ice bath 0.5 hour, forms buff mixed solution, continues
The 187ul NaBH now matched is added dropwise after ice bath 1 hour with liquid-transfering gun4Chlorine palladium acid is reduced into palladium colloidal sol by solution (0.5M), in system
Mixed liquor rapidly goes to black, and sodium hydroxide solution (10.0g/100ml) 2ml is slowly added dropwise, and regulation system PH is 10.Finally plus
Enter 1.0g Beta zeolite, continues ice bath stirring 1 hour.
4th step collects gray product and is separated by solid-liquid separation, is washed, being dried to obtain dark gray solid product, in two stages
Product of roasting: the first stage is 400 DEG C of air atmosphere and roasts 4 hours that second stage uses 300 DEG C of hydrogen atmosphere reduction instead after cooling
3 hours.Collection obtains 1.85g Dark grey Pd-Beta solid product, is named as Pd-Beta crystal seed 1.
5th step repeats the 5th step in embodiment 1；The difference is that: without ageing directly by crystal seed-gelinite
System's hydrothermal crystallizing into stainless steel kettle.Crystallization time is changed to 120 hours, crystallization temperature is changed to 120 DEG C.
6th step, through cooling, centrifugation, washing, drying after crystallization completion, collection obtains 1.78g light grey solid particle.It is empty
Lower 350 DEG C of gas atmosphere roast 3 hours, use 300 DEG C of hydrogen atmosphere instead after cooling and restore 3 hours, obtain hud typed Pd@Beta points
Sub- sieve catalyst sample 3.
Embodiment 4
The first step weighs 0.11g sodium hydroxide, 0.47g sodium metaaluminate solid is added to equipped with 19.0g tetraethyl hydroxide
It is stirred to clarify in the three-necked flask of ammonium salt solution.6.0g white carbon black is slowly added into solution, is formed after being vigorously stirred 0.5 hour
White mixture gel.Mixture gel obtained is transferred to 140 DEG C of hydro-thermal static crystallization 3 days in stainless steel kettle, crystallization is complete
Cheng Houjing is cooling, centrifugation, washs, is dry, and collection obtains white solid product.
The Beta zeolite seed crystal product of collection is placed into Muffle furnace by second step, and 550 DEG C roast 5 hours, to be cooled
After open Muffle furnace, collect sample and be sized to 100 mesh hereinafter, obtaining the thin sprills Beta product of 3.25g white.
The 5th step in embodiment 3 is repeated, palladium presoma is uniformly mixed with Beta zeolite；
4th step collects product and is separated by solid-liquid separation, is washed, being dried to obtain gray solid product, and collection obtains 1.48g depth
Grey Pd-Beta solid product, is named as Pd-Beta crystal seed 2.
5th step repeats the 5th step in embodiment 1, the difference is that, Aging Temperature is changed to 80 DEG C, digestion time
It is 10 hours.
6th step, through cooling, centrifugation, washing, drying after crystallization completion, collection obtains 1.70g light grey solid particle.Through
Lower 350 DEG C of air atmosphere roast 3 hours, use 300 DEG C of reductase 12 hours of hydrogen atmosphere instead after cooling, obtain hud typed Pd@Beta
Molecular sieve catalyst sample 4.
Embodiment 5
Embodiment 1 is repeated, by SiO in the silica-alumina gel of the 5th step2/Al2O330,50 are changed to from 40, obtained product is
Beta zeolite, calculating relative crystallinity by XRD spectra result is respectively 51.7%, 86.0%.
Embodiment 6
Embodiment 1 is repeated, the seed load of the 5th step is changed to 4%, 6%, 8%, 12%, 14% from 10wt.%, by
The product that XRD spectra is analyzed is Beta zeolite, calculate its relative crystallinity be respectively 30.5%, 55.7%, 85.1%,
93.7%, 91.1%.
Embodiment 7
Embodiment 1 is repeated, the digestion time of the 5th step is changed to 5 hours and 10 hours respectively, in identical crystallization temperature
At 130 DEG C, it will be respectively 36 hours and 44 hours that the relative crystallinity of product, which reaches highest crystallization time,.
Comparative example 1
According to method described in embodiment 1, it will directly handle to obtain Pt-Beta through urea precipitation method, not add as crystal seed
Enter into Primogel, reduction obtains gray solid fine catalyst under the identical roasting condition of embodiment 1, is named as Pt-
Beta。
Comparative example 2
It, directly will be through NaBH according to method described in embodiment 34Processing obtains depth under identical roasting condition after reduction
Gray solid fine catalyst, is named as Pd-beta.
Application examples 1
Resulting core-shell type zeolite molecular sieve catalyst sample 1~4 and 1~2 sample of comparative example are added to 50ml kettle
Experiment in formula high-pressure reactor, for methyl phenyl ethers anisole hydrogenation deoxidation.Catalyst amount is 50mg, solvent decahydronaphthalene 20mL, substrate
Methyl phenyl ethers anisole 5mmol.Using remaining air in nitrogen purging 3 removal systems of reaction kettle before reaction, when temperature is raised to target temperature
It is passed through hydrogen when spending and starts timing.Reaction condition: revolving speed 700rpm, 200 DEG C of reaction temperature, the reaction time 4 hours, hydrogen pressure
Power 1.0Mpa.Product is qualitative to use Agilent gas chromatograph-mass spectrometer, and product quantitatively uses Agilent gas chromatograph.
Claims (4)
1. a kind of preparation method of hud typed Beta molecular sieve catalyst, which is characterized in that steps are as follows:
Step 1: using urea precipitation method or NaBH4Reduction method loads in Beta molecular sieve seed according to noble metal
The ratio of 0.5wt.%~2wt.% uniformly contacts noble metal precursor body with the Beta molecular sieve seed of addition in the solution；
The SiO of inner layer B eta molecular sieve2/Al2O3Molar ratio is 22.0~31.8, before the molecular sieve carried required noble metal of inner layer B eta
Driving body salt is chloroplatinic acid or palladium chloride；The SiO of outer layer Beta molecular sieve2/Al2O3Molar ratio is 9.8-13.0；
Step 2: collecting product, it is separated by solid-liquid separation, 450 DEG C of roasting 3h, obtaining that treated, Beta molecular sieve seed is Pt-
Beta；
Step 3: silicon source, sodium hydroxide are dissolved in respectively in deionized water after formation clear solution, the two after mixing, is delayed
Slowly desired amount of silicon source is added thereto, forms homogeneous gel；It is under conditions of being not higher than 120 DEG C of crystallization temperatures, its is close
Envelope ageing stands 0~10 hour；
Silicon source in the raw material, silicon source, sodium hydroxide and deionized water original mole of composition are as follows: SiO2/Al2O3=40~
60, Na2O/SiO2=0.30~0.42, TEA+/SiO2=0~0.10, H2O/SiO2=20~35；
Step 4: being added to second step according to required amount through aging process by the Beta molecular sieve seed that processing obtains
It stirs evenly in gel, then shifts mixed gel in stainless steel kettle, incubation water heating crystallization 36 under the conditions of 120~140 DEG C~
120 hours；After crystallization, product is collected through separation of solid and liquid, washing, drying, obtains the nucleocapsid of cladding noble metal nano particles
Type Beta molecular sieve catalyst.
2. preparation method according to claim 1, which is characterized in that in the 4th step, second step obtains Pt-Beta as brilliant
The additive amount of kind is 6wt.%~12wt.% of the 4th step gross mass.
3. preparation method according to claim 1 or 2, which is characterized in that the silicon source is white carbon black, silica solution or just
Silester；Silicon source is sodium metaaluminate or aluminium powder.
4. a kind of hud typed Beta molecular sieve catalyst is applied in the reaction of lignin derivative aromatic compound.
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| CN112844456A (en) * | 2021-01-21 | 2021-05-28 | 中国工程物理研究院核物理与化学研究所 | Preparation method and application of core-shell type metal zeolite catalyst |
| CN113385217A (en) * | 2021-06-25 | 2021-09-14 | 中山大学 | Palladium-based core-shell structure catalyst for catalytic combustion of low-concentration methane and preparation method thereof |
| CN113649064A (en) * | 2021-07-22 | 2021-11-16 | 中国石油大学(北京) | Zeolite molecular sieve loaded metal catalyst and synthesis method and application thereof |
| CN114367307A (en) * | 2022-01-19 | 2022-04-19 | 太原理工大学 | Synthesis method of M @ SSZ-13@ Nanobeta with core-shell structure |
| CN114931971A (en) * | 2022-04-26 | 2022-08-23 | 榆林学院 | Nickel nanocluster supported intercrystalline mesoporous zeolite catalyst and preparation method and application thereof |
| CN115555044A (en) * | 2022-10-10 | 2023-01-03 | 无锡威孚环保催化剂有限公司 | Preparation method of catalyst for NOx pollutants of hydrogen internal combustion engine |
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