CN105749959A - High-silica molecular sieve catalyst used for nitrous oxide decomposition - Google Patents
High-silica molecular sieve catalyst used for nitrous oxide decomposition Download PDFInfo
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
The invention discloses a high-silica molecular sieve catalyst used for nitrous oxide decomposition and a preparation method for the high-silica molecular sieve catalyst. The method comprises the following steps: (1) alkali modification treatment on a molecular sieve; (2) acid modification treatment on the molecular sieve; (3) first metal modification on the molecular sieve; (4) second modification on the molecular sieve; a first metal salt and a second metal salt are selected from one or several of nitrate, sulfate and carbonate of transition metals and noble metals. The catalyst produced by the method disclosed by the invention shows better performance and stability, and moreover, the method is convenient for large-scale industrial production, and production cost is low.
Description
Technical field
The present invention relates to field catalyst field, be specifically related to a kind of high-silica zeolite catalyst for nitrous oxide.
Background technology
Nitrous oxide is considered as nontoxic gas for a long time.But the research of recent years shows, N2O can not only heavy damage ozone layer, and there is very strong greenhouse effect.N2The Global Warming potential (GWP) of O is CO respectively2310 times, CH415 times.And, it is highly stable in troposphere, and average life is long.Therefore, exploitation can efficient removal N2Technology and the method for O have important practical significance.
N2The topmost industrial source of O includes the production of the fatty acid such as nitric acid, adipic acid, chemical fertilizer production and is the industrial process of oxidant with nitric acid.In adipic acid, often produce the appointment of 1t adipic acid and produce 0.27tN2O, its discharge capacity accounts for the 10% of whole world total amount.Further, the tail gas of discharge exists the miscellaneous QI component H of higher concentration2O、NO、O2Deng.By N under the effect of catalyst2O catalytic decomposition is N2And O2It is considered as the most promising N2O controls technology.
That studied at present is applied to N2The catalyst of O catalytic decomposition mainly includes Engineering of Supported Metal Oxide Catalysts, such as MnOx/MgO(US5705136)；Brucite Derived Mixed Oxides, such as Rh0.01Mg0.71Al0.28O1.145(EP1262224B1)；Spinel structure composite oxides, such as CuAlO4(US6723295B1).Although these catalysis materials have significantly high activity, but the existence of miscellaneous QI component can make above-mentioned rapid catalyst deactivation or significantly inhibit its activity.
Research shows, molecular sieve catalyst, has uniform pore structure, good heat stability, cheap cost.And at the H of higher concentration2O、NO、O2、SO2Existence under, also have excellence stability and activity.These find to produce N in tail gas for eliminating2The discharge of O provides great desired solution.
China Patent Publication No. CN101664694A discloses a kind of N adopting infusion process to prepare2The molecular sieve carried cobalt composite oxide catalyst of O catalytic decomposition, about 550 DEG C are decomposed N completely2O.Owing to the at high temperature roasting of this catalyst prepares (500～1000 DEG C), catalyst has good heat-resisting quantity.
China Patent Publication No. CN102380410A discloses a kind of catalytic decomposition N2The ferro-cobalt bimetallic catalyst of O.The expression formula of catalyst is: CoFe-MOR.This catalyst passes through two step aqueous solution ion exchange load C o and Fe, can realize N at 430 DEG C2The conversion ratio of O gas 100%, and stability is higher.
China Patent Publication No. CN101450322A discloses a kind of employing FeCl3As precursor, prepare Fe/ZSM-5 catalysis material by the method for solid state ion exchange.And increase active sites by adding the method for Ga, B, P and high-temperature roasting.The catalyst that the method obtains avoids the generation of bulk inertia ferrum oxide, reproducible.N can be realized at 530 DEG C2The conversion ratio of O reaches 100%, after adding Ga, just can reach the conversion ratio of 98% at 480 DEG C.But, the stability for catalyst is mentioned.
In sum, molecular sieve catalyst is at N2The direct cartalytic decomposition effect of O shows good application prospect, however how to prepare high activity, the catalyst of high stability is crucial.
Summary of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of high-silica zeolite catalyst for nitrous oxide, to overcome in prior art not high for the catalyst activity of catalytic oxidation Asia nitrogen decomposition, that stability is bad defect.
To achieve these goals or other purposes, the present invention is achieved by the following technical solutions.
The preparation method of a kind of molecular sieve catalyst for nitrous oxide, described method comprises the steps:
1) alkali modification of molecular sieve processes: molecular sieve and aqueous slkali are mixed and stirred for, and after stirring terminates, washing is extremely neutral, dries the molecular sieve carrier obtaining alkali modification；
2) the sour modification of molecular sieve: the molecular sieve carrier of alkali modification and acid solution are mixed and stirred for, after stirring terminates, washing is extremely neutral, dries roasting and obtains the molecular sieve carrier that soda acid is modified；
3) the first of molecular sieve is metal-modified: the molecular sieve carrier modified by soda acid and the first aqueous metal salt are mixed and stirred for, and stirring terminates rear filtration washing to neutral, dries roasting and obtains the first metal-modified molecular sieve；
4) the second of molecular sieve is metal-modified: will mixing water bath method in the first metal-modified molecular sieve and the second aqueous metal salt, then dry roasting and namely obtain the molecular sieve catalyst of bimetallic load；
Described first slaine and described second slaine are one or more in transition metal and the nitrate of noble metal, sulfate and carbonate.
Preferably, described transition metal is ferrum, cobalt, copper or nickel.
Preferably, described noble metal is platinum, ruthenium, palladium or iridium.
Preferably, described first slaine is one or more in the nitrate of Fe, sulfate and carbonate.
Preferably, when described second slaine is one or more in the nitrate of Co, sulfate and carbonate.
Preferably, step 1) described in one or more in MFI, Beta and MOR of molecular screening, the content of Si and Al atom in described molecular sieve is converted into SiO according to atomic molar number2Molecule and Al2O3Molecule, described SiO2Molecule and Al2O3The mol ratio of molecule is 150～450.It is highly preferred that described molecular sieve is ZSM-5 molecular sieve or Beta molecular sieve.
Preferably, step 1) described in the concentration of aqueous slkali be 0.05～2mol/L, described aqueous slkali is NaOH, KOH, Na2CO3And K2CO3In one or more aqueous solution.
Preferably, in reference count for the volume of described aqueous slkali, step 1) described in the dosage of molecular sieve be 0.005～1.5g/mL.
Preferably, step 1) in the temperature of mix and blend be 40～90 DEG C, drying temperature is 60～140 DEG C.
Preferably, drying temperature is 120 DEG C.
Preferably, step 1) in time of mix and blend be at least 1h.
Preferably, step 2) described in the concentration of acid solution be 0.05～2mol/L, described acid solution is HNO3、HCl、CH3COOH and H2CO3In one or more aqueous solution.
Preferably, step 2) in, in reference count for the volume of described acid solution, the dosage of described molecular sieve is 0.04～0.06g/mL.It is highly preferred that the dosage of described molecular sieve is 0.05g/mL.
Preferably, step 2) in mix and blend temperature be 20～60 DEG C, drying temperature is 60～140 DEG C.It is highly preferred that described drying temperature is 120 DEG C.
Preferably, step 2) in time of mix and blend be at least 2h.
Preferably, step 2) in sintering temperature be 550～650 DEG C.It is highly preferred that step 2) in sintering temperature be 600 DEG C.
Preferably, step 3) in, the concentration of described first aqueous metal salt is 0.05～1mol/L；Step 4) in, the concentration of described second aqueous metal salt is 0.05～2mol/L.
Preferably, step 3) in, in reference count for the cumulative volume of described first aqueous metal salt, the mass body volume concentrations of described molecular sieve is 0.04～0.06g/mL.It is highly preferred that the mass body volume concentrations of described molecular sieve is 0.04～0.06g/mL.
Preferably, step 3) in, drying temperature is 100～150 DEG C.It is highly preferred that drying temperature is 120 DEG C.
Preferably, step 3) in, sintering temperature is 550～650 DEG C.It is highly preferred that sintering temperature is 600 DEG C.
Preferably, step 4) in, in reference count for the cumulative volume of described second aqueous metal salt, the mass body volume concentrations of described molecular sieve is 0.4～0.6g/mL.
Preferably, step 4) in, drying temperature is 100～150 DEG C.It is highly preferred that step 4) in, drying temperature is 120 DEG C.
Preferably, step 4) in, sintering temperature is 550～650 DEG C.It is highly preferred that step 4) in, sintering temperature is 600 DEG C.
Invention additionally discloses a kind of molecular sieve catalyst for nitrous oxide catalytic decomposition, prepared by including method described above.
The invention also discloses the molecular sieve catalyst as described above purposes in nitrous oxide.
The preparation method of the catalyst disclosed in the present invention has the advantages that
A kind of method of modifying of the high-silica zeolite carrier of the present invention, by the acid-base pretreatment amorphous species to molecular sieve, particle size, the acidic site of pore passage structure and carrier is adjusted, be conducive to slaine presoma in the first process to be fully diffused in duct, improve ion-exchange degree.Furthermore it is possible to improve in the second process and dipping process, the high dispersion of active component.The catalyst carrier simultaneously obtained after acid-alkali treatment still retains high silicon characteristic, has good hydrothermal stability.Thus catalyst shows good performance and stability.Its method is prone to large-scale industrial production, and production cost is low.
Accompanying drawing explanation
The catalyst Z 150-a that Fig. 1 is the catalyst Z 150-D prepared in embodiment 4 and comparative example 1 prepares is to N2The performance map of O decomposition reaction.
Detailed description of the invention
By particular specific embodiment, embodiments of the present invention being described below, those skilled in the art the content disclosed by this specification can understand other advantages and effect of the present invention easily.
Refer to Fig. 1.Notice, the structure of this specification institute accompanying drawings depicted, ratio, size etc., all only in order to coordinate the disclosed content of description, understand for those skilled in the art and read, it is not limited to the enforceable qualifications of the present invention, therefore do not have technical essential meaning, the adjustment of the modification of any structure, the change of proportionate relationship or size, under not affecting effect that the present invention can be generated by and the purpose that can reach, all should still drop on disclosed technology contents and obtain in the scope that can contain.Simultaneously, in this specification cited as " on ", D score, "left", "right", " centre " and " one " etc. term, it is merely convenient to understanding of narration, and it is not used to limit the enforceable scope of the present invention, the change of its relativeness or adjustment, changing under technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1
Choose SiO2Molecule and Al2O3Molecule mol ratio is the ZSM-5 molecular sieve of 150, the NaOH solution of preparation 0.05mol/L, and the dosage of molecular sieve and aqueous slkali volume ratio are 0.005g/mL, molecular sieve is joined in aqueous slkali, controlling aqueous slkali temperature at 40 DEG C, process 1h, filtration washing to effluent is neutral.Dry a whole night at 120 DEG C, obtain the molecular sieve carrier of alkali modification.
Preparation 0.05mol/LHNO3Solution, is 0.05g/mL by the proportioning of molecular sieve and acid solution, joins in acid solution by alkali modification molecular sieve carrier, stirs 2h at 20 DEG C, and filtration washing to effluent is neutral.Drying a whole night at 120 DEG C, then roasting 4h at 600 DEG C, obtains the molecular sieve carrier that soda acid is modified.
0.05mol/L is containing Fe in preparation3+Aqueous solution, by molecular sieve with containing Fe3+The proportioning of aqueous solution be 0.05g/mL, modified molecular sieve carrier is joined containing Fe3+Aqueous solution in.At room temperature stirring 24h, filtration washing to effluent is neutral.Dry a whole night at 120 DEG C, then at 600 DEG C roasting 4h, obtain the modified molecular sieve of Fe.
0.05mol/L is containing Co in configuration2+Aqueous solution, by molecular sieve with containing Co2+The proportioning of aqueous solution be 0.5g/mL, the molecular sieve that the Fe obtained is modified be impregnated in containing Co2+Aqueous solution in, be sufficiently stirred for, be then evaporated under the water-bath of 60 DEG C, then dry a whole night at 120 DEG C, then at 600 DEG C roasting 4h, obtain the modified molecular sieve catalyst of Co, Fe, sample number into spectrum is Z150-A.
Embodiment 2
The NaOH solution of 0.05mol/L, with embodiment 1, is simply changed into the NaOH solution of 2mol/L by preparation process, and sample number into spectrum is Z150-B.
Embodiment 3
Preparation process is with embodiment 1, and the dosage and the aqueous slkali volume ratio that are molecular sieve are that 0.005g/mL changes 1.5g/mL into, and sample number into spectrum is Z150-C.
Embodiment 4
Preparation process, with embodiment 1, simply will control base extraction temperature at 40 DEG C, change into control base extraction temperature at 90 DEG C, and sample number into spectrum is Z150-D.
Embodiment 5
Preparation process is with embodiment 1, simply by 0.05mol/LHNO3Solution changes 2mol/LHNO into3Solution, sample number into spectrum is Z150-E.
Embodiment 6
Controls acid treatment temperature, with embodiment 1, is simply 20 DEG C by preparation process, changes that to control acid treatment temperature be 60 DEG C into, and sample number into spectrum is Z150-F.
Embodiment 7
The controls acid treatment time, with embodiment 1, is simply 2h by preparation process, changes that to control the acid treatment time be 12h into, and sample number into spectrum is Z150-G.
Embodiment 8
Si/Al ratio, with embodiment 1, is simply the ZSM-5 molecular sieve of 150, changes the ZSM-5 molecular sieve that Si/Al ratio is 450 into by preparation process, and sample number into spectrum is Z450-A.
Embodiment 9
Si/Al ratio, with embodiment 1, is simply the ZSM-5 molecular sieve of 150, changes the Beta molecular sieve that Si/Al ratio is 150 into by preparation process, and sample number into spectrum is B450-A.
Embodiment 10
Preparation process, with embodiment 1, simply will prepare 0.05mol/L containing Fe3+Aqueous solution, change into preparation 1mol/L containing Fe3+Aqueous solution, sample number into spectrum is Z150-H.
Embodiment 11
Preparation process, with embodiment 1, simply will prepare 0.05mol/L containing Co2+Aqueous solution, change into preparation 2mol/L containing Co2+Aqueous solution, sample number into spectrum is Z150-I.
Embodiment 12
Choose SiO2Molecule and Al2O3Molecule mol ratio is the ZSM-5 molecular sieve of 150, the NaOH solution of preparation 0.05mol/L, and the dosage of molecular sieve and aqueous slkali volume ratio are 0.005g/mL, molecular sieve is joined in aqueous slkali, controlling aqueous slkali temperature at 40 DEG C, process 1h, filtration washing to effluent is neutral.Dry a whole night at 120 DEG C, obtain the molecular sieve carrier of alkali modification；
Preparation 0.05mol/LHNO3Solution, is 0.05g/mL by the proportioning of molecular sieve and acid solution, joins in acid solution by alkali modification molecular sieve carrier, stirs 2h at 20 DEG C, and filtration washing to effluent is neutral.Drying a whole night at 120 DEG C, then roasting 4h at 600 DEG C, obtains the molecular sieve carrier that soda acid is modified；
0.05mol/L is containing Co in preparation2+Aqueous solution, by molecular sieve with containing Co2+The proportioning of aqueous solution be 0.05g/mL, modified molecular sieve carrier is joined containing Co2+Fe3+Aqueous solution in.At room temperature stirring 24h, filtration washing to effluent is neutral.Dry a whole night at 120 DEG C, then at 600 DEG C roasting 4h, obtain the modified molecular sieve of Fe.
0.05mol/L is containing Fe in configuration3+Aqueous solution, by molecular sieve with containing Fe3+The proportioning of aqueous solution be 0.5g/mL, the molecular sieve that the Co obtained is modified be impregnated in containing Fe3+Aqueous solution in, be sufficiently stirred for, be then evaporated under the water-bath of 60 DEG C, then dry a whole night at 120 DEG C, then at 600 DEG C roasting 4h, obtain the modified molecular sieve catalyst of Co and Fe.
Comparative example 1
Choosing the ZSM-5 molecular sieve material that Si/Al ratio is 150,0.05mol/L is containing Fe in preparation3+Aqueous solution, by molecular sieve with containing Fe3+The proportioning of aqueous solution be 0.05g/mL, mother matrix molecular sieve carrier is joined containing Fe3+Aqueous solution in.At room temperature stirring 24h, filtration washing to effluent is neutral.Dry a whole night at 120 DEG C, then at 600 DEG C roasting 4h, obtain the modified molecular sieve of Fe.
0.05mol/L is containing Co in configuration2+Aqueous solution, by molecular sieve with containing Co2+The proportioning of aqueous solution be 0.5g/mL, the molecular sieve of the Fe load obtained be impregnated in containing Co2+Aqueous solution in, be sufficiently stirred for, be then evaporated under the water-bath of 60 DEG C, then dry a whole night at 120 DEG C, then at 600 DEG C roasting 4h, obtain the modified molecular sieve catalyst of Co, Fe, sample number into spectrum is Z150-a.
Comparative example 2
Si/Al ratio, with comparative example 1, is simply the ZSM-5 molecular sieve of 150, changes the ZSM-5 molecular sieve that Si/Al ratio is 450 into by preparation process, and sample number into spectrum is Z450-a.
Comparative example 3
Si/Al ratio, with comparative example 1, is simply the ZSM-5 molecular sieve of 150, changes the Beta molecular sieve that Si/Al ratio is 150 into by preparation process, and sample number into spectrum is B450-a.
Comparative example 4
Preparation process, with comparative example 1, simply will prepare 0.05mol/L containing Fe3+Aqueous solution, change into preparation 1mol/L containing Fe3+Aqueous solution, sample number into spectrum is Z150-h.
Comparative example 5
Preparation process, with comparative example 1, simply will prepare 0.05mol/L containing Co2+Aqueous solution, change into preparation 2mol/L containing Co2+Aqueous solution, sample number into spectrum is Z150-i.
Catalyst performance evaluation condition:
By 0.4g embodiment 1～11, the sample of comparative example 1～5 is respectively charged in following fixed-bed quartz reactor.Catalysis material first purges 0.5h in 550 DEG C of pure Ar (60ml/min) atmosphere, is cooled to reacting initial temperature (about 275 DEG C), switches to hybrid reaction gas (5000ppmN2O+5%O2+ Ar Balance Air), air speed is approximately 30000h-1.The heating schedule of reacting furnace is: initial reaction temperature 275 DEG C, is an intensification point every 25 DEG C, and heating rate is 2.5 DEG C/min, and reaction carries out sample analysis after arriving stable state, and result is as shown in table 1.
T in table 150(DEG C) represents that in reaction, conversion ratio reaches temperature spot corresponding when 50%.T90(DEG C) represents that in reaction, conversion ratio reaches temperature spot corresponding when 90%.As can be seen from Table 1, in the present invention, catalyst is compared with catalyst in comparative example, just can reach identical conversion ratio at lower temperatures.
The N of table 1 embodiment 1～11 and comparative example 1～5 molecular sieve catalyst2O decomposability
Catalyst stability appreciation condition:
When simulated condition, do the high-silica zeolite hydrothermal stability that long period experimental evaluation is modified.Concrete appreciation condition is as follows: 0.4g catalyst Z 150-A, Z150-D, Z450-A and B150-A are respectively charged in above-mentioned fixed-bed quartz reactor.Catalysis material first purges 0.5h in 550 DEG C of pure Ar (60ml/min) atmosphere, is cooled to 400 DEG C, 425 DEG C, 415 DEG C, 390 DEG C respectively and switches to hybrid reaction gas (5000ppmN2O+5%O2+ 500ppmNO+5%H2O+Ar Balance Air), air speed is approximately 30000h-1.Reaction is analyzed after arriving stable state, and the response time continues 100h, and result is as shown in table 2.
The stability of molecular sieve when table 2 simulated condition
It is shown that through the molecular sieve catalyst of soda acid modified bimetallic load, when simulated condition through the operation of 100h, the activity of molecular sieve catalyst remains stable for, and obvious inactivation does not occur.This shows that molecular sieve catalytic material prepared by the present invention can be applicable in industry.
The catalyst Z 150-a that Fig. 1 is the catalyst Z 150-D prepared in embodiment 4 and comparative example 1 prepares is to N2The performance map of O decomposition reaction.Upper it can be seen that adopt the catalyst that the method in the present invention obtains to have more high reaction activity by figure.
Above-described embodiment is illustrative principles of the invention and effect thereof only, not for the restriction present invention.Above-described embodiment all under the spirit and category of the present invention, can be modified or change by any those skilled in the art.Therefore, art has usually intellectual such as modifying without departing from all equivalences completed under disclosed spirit and technological thought or change, must be contained by the claim of the present invention.
Claims (10)
1., for a preparation method for the molecular sieve catalyst of nitrous oxide, described method comprises the steps:
1) alkali modification of molecular sieve processes: molecular sieve and aqueous slkali are mixed and stirred for, and stirring is filtered after terminating and washs to neutral, dries the molecular sieve carrier obtaining alkali modification；
2) the sour modification of molecular sieve: the molecular sieve carrier of alkali modification and acid solution are mixed and stirred for, stirring is filtered after terminating and washs to neutral, dries roasting and obtains the molecular sieve carrier that soda acid is modified；
3) the first of molecular sieve is metal-modified: the molecular sieve carrier modified by soda acid and the first aqueous metal salt are mixed and stirred for, and stirring terminates rear filtration washing to neutral, dries roasting and obtains the first metal-modified molecular sieve；
4) the second of molecular sieve is metal-modified: the first metal-modified molecular sieve and the second aqueous metal salt carry out mixing water bath method, then dries roasting and namely obtain the molecular sieve catalyst of bimetallic load；
Described first slaine and described second slaine are one or more in transition metal and the nitrate of noble metal, sulfate and carbonate.
2. as claimed in claim 1 preparation method, it is characterised in that: step 1) described in one or more in MFI, Beta and MOR of molecular screening, the content of Si and Al atom in described molecular sieve is converted into SiO according to atomic molar number2Molecule and Al2O3Molecule, described SiO2Molecule and Al2O3The mol ratio of molecule is (150～450): 1.
3. as claimed in claim 1 preparation method, it is characterised in that: step 1) described in the concentration of aqueous slkali be 0.05～2mol/L, described aqueous slkali is NaOH, KOH, Na2CO3、K2CO3In one or more aqueous solution.
4. as claimed in claim 1 preparation method, it is characterised in that: in reference count for the volume of described aqueous slkali, step 1) described in the dosage of molecular sieve be 0.005～1.5g/mL.
5. as claimed in claim 1 preparation method, it is characterised in that: step 1) in whipping temp be 40～90 DEG C, drying temperature is 60～140 DEG C.
6. as claimed in claim 1 preparation method, it is characterised in that: step 2) described in the concentration of acid solution be 0.05～2mol/L, described acid solution is HNO3、HCl、CH3COOH and H2CO3In one or more aqueous solution.
7. as claimed in claim 1 preparation method, it is characterised in that: step 2) in whipping temp be 20～60 DEG C, drying temperature is 60～140 DEG C.
8. preparation method as claimed in claim 1, it is characterised in that: step 3) in, the concentration of described first aqueous metal salt is 0.05～1mol/L；Step 4) in, the concentration of described second aqueous metal salt is 0.05～2mol/L.
9. for a molecular sieve catalyst for nitrous oxide catalytic decomposition, the arbitrary described method of claim 1～8 prepare.
10. molecular sieve catalyst purposes in nitrous oxide as claimed in claim 9.
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| CN112973777A (en) * | 2021-02-23 | 2021-06-18 | 浙江浙能技术研究院有限公司 | Low Ir-loaded catalyst for efficiently decomposing nitrous oxide and preparation method thereof |
| CN115430453A (en) * | 2022-09-27 | 2022-12-06 | 辽宁大学 | Low-temperature catalytic decomposition of N 2 O transition metal oxide catalyst and preparation method and application thereof |
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| CN112973777A (en) * | 2021-02-23 | 2021-06-18 | 浙江浙能技术研究院有限公司 | Low Ir-loaded catalyst for efficiently decomposing nitrous oxide and preparation method thereof |
| CN115430453A (en) * | 2022-09-27 | 2022-12-06 | 辽宁大学 | Low-temperature catalytic decomposition of N 2 O transition metal oxide catalyst and preparation method and application thereof |
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| CN105749959B (en) | 2018-05-15 |
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