CN106799255A - The preparation method and applications of the molecular sieve catalysts of one-step synthesis method Cu SSZ 39 - Google Patents

The preparation method and applications of the molecular sieve catalysts of one-step synthesis method Cu SSZ 39 Download PDF

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CN106799255A
CN106799255A CN201710099479.2A CN201710099479A CN106799255A CN 106799255 A CN106799255 A CN 106799255A CN 201710099479 A CN201710099479 A CN 201710099479A CN 106799255 A CN106799255 A CN 106799255A
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ssz
molecular sieve
silicon source
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sieve catalysts
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李涛
范驰
陈真
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Huazhong University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
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Abstract

The present invention is used with the molecular sieve catalysts of double template one-step synthesis method Cu SSZ 39, it is 2.00~5.00wt.% by controlling the input ratio of copper sulphate TEPA and organic formwork agent to regulate and control copper load capacity, simultaneously control the silica alumina ratio of USY reach control product silica alumina ratio be 4.5~16.4, obtain that there is crystallinity higher, excellent catalysis activity, the molecular sieve catalysts of Cu SSZ 39 of hydrothermal stability, it is adaptable to which diesel vehicle post-processes Urea SCR system catalysts and stationary source NH3Oxynitrides purification process in SCR.Compared with existing synthetic method, with process is simple, it is to avoid ammonium nitrate and copper salt solution ion exchange and calcine technology is used for multiple times, overcome traditional one-step synthesis must be by the shortcoming of later stage ion-exchange process load active component.The present invention uses cheap template, considerably reduces production cost, is conducive to industry to amplify application.

Description

The preparation method and applications of one-step synthesis method Cu-SSZ-39 molecular sieve catalysts
Technical field
The invention belongs to chemical industry and field of Environment Protection, it is related to the preparation of Cu-SSZ-39 molecular sieve catalysts, and in particular to a kind of The method that Cu-SSZ-39 catalyst is prepared with double template one-step method, and the catalyst that the method is prepared is used for diesel oil Oxynitrides SCR (NH3-SCR) process in tail gas.
Background technology
Nitrogen oxides is mainly derived from plant gas and motor-vehicle tail-gas as a kind of main atmosphere pollution.Wherein, Exhaust gas from diesel vehicle nitrogen oxides (NOx) pollution have become most one of distinct issues in China's atmosphere pollution.As environment is asked Increasingly highlighting for topic is increasingly improved with environmentally friendly laws and regulations for exhaust gas from diesel vehicle emission request, administers exhaust gas from diesel vehicle nitrogen oxidation Thing turns into the hot issue of today's society.Ammonia SCR (NH3- SCR) eliminate nitrogen oxides (NOx) with its efficiently, The advantage of low cost turns into denitration technology most potential and most widely used at present.Traditional NH3- SCR is with V2O5/WOx-TiO2 It is catalyst, but such catalyst activity temperature window is narrow, and hydrothermal stability is poor, is easily poisoned and itself just has toxicity.From Iwamoto in 1986 etc. has found that Cu loads ZSM-5 is that a kind of efficient SCR eliminates NOxAfter catalyst, development of metallic based molecular sieve (Cu/Fe-ZSM-5, Cu/Fe-Beta etc.) catalyst turns into one of study hotspot hereafter.But this two kinds of molecular sieves are passing through Due to the generation of dealumination process after high temperature hydrothermal aging, hydrothermal stability is poor.
According to nearest document report, the molecular sieve (SSZ-13 and SAPO-34) with CHA structure of Cu loads with it is traditional Cu-ZSM-5, Cu-Beta are compared, and Cu-CHA molecular sieves have more excellent SCR catalyst activity and hydrothermal stability (J.Catal., 2010,275,187-190, U.S.Patent, 0,226,545,2008).This comes from the molecular sieve of CHA structure Have a less octatomic ring pore passage structure, active Cu ions preferentially with double hexatomic rings on three oxygen atom ligands so that greatly Improve its hydrothermal stability.Corma in 2012 etc. report first with and CHA molecular sieve similar structures SSZ-39 molecules Have after sieve loaded Cu the SCR catalysis activity and hydrothermal aging more excellent compared with Cu-CHA molecular sieves (Chem.Commun., 2012,48,8264–8266).Then, MM Malins (CN104520548A), Tsuneji Sano (J.Mater.Chem.A, 2015,3,857-865) reported using distinct methods and template with Comar etc. (Chem.Commun., 2015,51,11030) Cu-SSZ-39 prepared by agent has excellent catalysis activity and hydrothermal stability in SCR.But in these catalyst preparation sides There is a series of problems in method, such as MM Malins using the tetramethyl piperidine of template 1,1,3,5- drone first synthesize Na-SSZ-39 Cu-SSZ-39, Comar etc. are obtained by ion exchange or infusion process afterwards and utilize N, N- dimethyl -3,5- lupetidines drone and TEPA as double template use one-step synthesis method Cu-SSZ-39, wherein template piperidines drone it is cumbersome in building-up process, Cycle is more long, expensive raw material price needed for building-up process, is not suitable for commercial introduction application.And Tsuneji Sano etc. use template Agent tetraethyl hydroxide phosphine obtains Cu-SSZ-39 after first synthesizing Na-SSZ-39 for template by infusion process.And this two-step method system Standby Cu-SSZ-39 processes although template used dose it is relatively inexpensive, but subsequent process needs to be exchanged by ammonium and copper is exchanged, process Complicated compared with one-step method, the catalyst preparation cycle is long, and commercial Application is relatively costly.
Therefore the problem that synthesis Cu-SSZ-39 is present more than being directed to, develops a kind of preparation process simply, short preparation period, The cheap catalyst preparation process scheme of template seems and is even more important that this patent especially meets this requirement.
The content of the invention
An object of the present invention is to provide a kind of process is simple, does not need later stage ion-exchange process, environmental protection, section The about energy, the preparation method of the regulatable one-step synthesis method Cu-SSZ-39 of content of molecular sieve active ingredient copper and the catalyst In NH3Application in-SCR diesel car tail gas refining systems, is mainly used in selective catalysis and eliminates NO.The catalyst for being provided can Under range of reaction temperature (200~600 DEG C) wider, efficiently to eliminate NO (NO conversion ratios>80%).While high-temperature water vapor Degradation result shows：Catalyst is in 800 DEG C, H2Under the conditions of O content 10% after aging 12h, catalysis activity is without substantially big Amplitude declines, NO conversion ratios>90% active temperature windows are 250~550 DEG C.
In order to achieve the above object, this invention takes following technical scheme：
A kind of preparation method with double template one-step synthesis method Cu-SSZ-39, comprises the following steps：
(1) USY molecular sieve is prepared：By business NH4- Y zeolites dealuminzation under 700 DEG C of vapor, after at 75 DEG C, 0.74M's 4h is processed in sulfuric acid solution, silicon source and silicon source of the USY molecular sieve as synthesis Cu-SSZ-39 is obtained；
(2) by above-mentioned USY molecular sieve, NaOH, copper sulphate, TEPA and organic formwork agent sequentially add from Primogel is obtained after being sufficiently stirred in sub- water；The organic formwork agent be tetraethyl hydroxide phosphine, tetraethyl ammonium hydroxide and Any one in N, N- diisopropylethylamine.
(3) complete gel will be stirred to be placed in hydrothermal reaction kettle, crystallization 1~7 day, is cooled to room at 150~180 DEG C Temperature, through centrifugal filtration, deionized water washing, dries, and is calcined at 500~850 DEG C, obtains Cu-SSZ-39 molecular sieve catalysts.
In the method, using each reaction raw materials be as silicon source (silica) and silicon source (aluminum oxide) USY molecular sieve, Copper sulphate-TEPA, You Jimo, sodium oxide molybdena, water and template raw material addition are 1.0 according to mol ratio：0.1~1.0： 0~1.0：0.2~2.0：0.1~0.5：20~50 are fed intake, wherein the organic formwork agent is tetraethyl hydroxide phosphine, four Any one in ethyl ammonium hydroxide and N, N- diisopropylethylamine；Wherein silicon source and silicon source are USY molecular sieve, i.e., in this hair In bright method, raw material USY molecular sieve is both silicon source (silica) source, is also the source of silicon source (aluminum oxide).
The present invention is used with double template one-step synthesis method Cu-SSZ-39 molecular sieve catalysts, by controlling copper sulphate-four The input ratio regulation and control copper load capacity of the amine of ethene five and organic formwork agent is 2.00~5.00wt.%, while controlling the sial of USY Product silica alumina ratio is controlled for 4.5~16.4 than reaching, and obtains that there is crystallinity higher, excellent catalysis activity, hydrothermally stable The Cu-SSZ-39 molecular sieve catalysts of property.
The inventive method process is simple, do not need later stage ion-exchange process, environmental protection, energy saving, molecular sieve live Property component copper content controllable, the inventive method prepare Cu-SSZ-39 molecular sieve catalysts can apply to NH3- SCR diesel oil Tail gas cleaning system, is mainly used in selective catalysis and eliminates NO.Cu-SSZ-39 molecular sieve catalysts prepared by the inventive method NO (NO conversion ratios can be efficiently eliminated under range of reaction temperature (200~600 DEG C) wider>80%).High-temperature water steams simultaneously Vapour degradation result shows：Catalyst is in 800 DEG C, H2Under the conditions of O content 10% after aging 12h, catalysis activity is without obvious Significantly decline, NO conversion ratios>90% active temperature windows are 250~550 DEG C.The Cu-SSZ- that the inventive method is prepared 39 molecular sieve catalysts are applied to diesel vehicle and post-process Urea-SCR system catalysts and stationary source NH3Oxynitrides in-SCR Purification process.Compared with the method for existing synthesis Cu-SSZ-39, this synthetic method has process is simple, it is to avoid be used for multiple times Ammonium nitrate and copper salt solution ion exchange and calcine technology, overcoming traditional one-step synthesis must be by later stage ion exchange work The shortcoming of skill load active component.Compared with document report one-step synthesis method Cu-SSZ-39, phase is used in technical solution of the present invention To relatively inexpensive template, production cost is considerably reduced, be conducive to industry to amplify application.Prepared using the inventive method Cu-SSZ-39 molecular sieve catalysts excellent NH is kept in temperature window wider3- SCR catalysis activities, while having ten Divide excellent hydrothermally stable performance.
Brief description of the drawings
During Fig. 1 is embodiment 1,2 and 3, one-step method double template, ion-exchange and infusion process prepare Cu-SSZ-39's XRD, one-step method and two-step method successfully synthesize the SSZ-39 crystal formations of AEI structures as seen from the figure；
During Fig. 2 is embodiment 1,2 and 3, one-step method double template, ion-exchange and infusion process prepare Cu-SSZ-39's The XRD of aged samples, as seen from the figure 800 degrees Celsius of aging rear Cu-SSZ-39 remain in that complete AEI structures, crystallinity It is declined slightly compared with fresh sample；
Fig. 3 is the SEM figures of one-step method double template synthesis fresh sample Cu-SSZ-39 in embodiment 1, and it has regular Cubic；
Fig. 4 is the NO of the fresh sample catalyst of embodiment 1,2 and 3xConversion ratio evaluation figure；
Fig. 5 is embodiment 1,2 and 3 in 800 DEG C of NO of aged samples catalystxConversion ratio evaluation figure；
Contrasted from Fig. 4 and the figures of Fig. 5 two, Cu-SSZ-39 and two-step ion exchange prepared by one-step method double template The Cu-SSZ-39 prepared with infusion process is more or less the same, and is respectively provided with excellent fresh and aging activity
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
Take business NH4- Y (Si/Al=5.3) zeolite 10g, is placed in tube furnace the dealuminzation 4h under 700 DEG C of vapor, after will The Y type molecular sieve of this dealuminzation processes 4h in 75 DEG C of concentration are for the sulfuric acid solution of 0.74M, obtains USY molecular sieve as synthesis Cu- The silicon source and silicon source of SSZ-39.20g tetraethyls bromide phosphine is well mixed with 100g deionized waters, adds hydroxide ion to hand over afterwards Resin 10g is changed, the template tetraethyl phosphonium hydroxide needed for being filtrated to get synthesis Cu-SSZ-39 after stirring in water bath 3h at 30 DEG C. It is silica, aluminum oxide, copper sulphate-TEPA, You Jimo, sodium oxide molybdena, water and template raw material by each reaction raw materials Addition is 1.0 according to mol ratio：0.04：0.025：0.6：0.3：30 are fed intake, wherein the organic formwork agent is tetrem Base hydroxide phosphine, silicon source and silicon source are USY molecular sieve.Complete gel will be stirred and be placed in hydrothermal reaction kettle and reacted, reacted Room temperature is cooled to after, through centrifugal filtration, deionized water washing, is dried, calcined at 550 DEG C, obtain Cu-SSZ-39 molecular sieves Catalyst；
Embodiment 2
By each reaction raw materials be silica, aluminum oxide, You Jimo, sodium oxide molybdena, water and template raw material addition according to Mol ratio is 1.0：0.04：0.6：0.3：30 are fed intake, wherein the organic formwork agent be tetraethyl hydroxide phosphine, silicon source and Silicon source is USY molecular sieve.Complete gel will be stirred and be placed in hydrothermal reaction kettle and reacted, room temperature is cooled to after the completion of reaction, passed through Centrifugal filtration, deionized water are washed, dried, and are calcined at 550 DEG C, obtain Na-SSZ-39 molecular sieve catalysts.Take Na-SSZ- 39 molecular sieve 10g are placed in the ammonium nitrate solution that 500ml concentration is 1.0M, after 80 DEG C of oil bath 12h, distilled water washing and filtering, 110 DEG C dry 12h, repeat above step and obtain NH4- SSZ-39 molecular sieves.By 5g NH4- SSZ-39 molecular sieves add 5ml dissolvings 0.625g Cu(CH3COO)2The aqueous solution in, ultrasonic 2h, the then unnecessary moisture of rotary evaporation at 50 DEG C, 110 DEG C of dryings 12h, after 550 DEG C of roasting temperature 4h, obtains the Cu-SSZ-39 molecular sieves that Cu contents are 5%.
Embodiment 3
By each reaction raw materials be silica, aluminum oxide, You Jimo, sodium oxide molybdena, water and template raw material addition according to Mol ratio is 1.0：0.04：0.6：0.3：30 are fed intake, wherein the organic formwork agent be tetraethyl hydroxide phosphine, silicon source and Silicon source is USY molecular sieve.Complete gel will be stirred and be placed in hydrothermal reaction kettle and reacted, room temperature is cooled to after the completion of reaction, passed through Centrifugal filtration, deionized water are washed, dried, and are calcined at 550 DEG C, obtain Na-SSZ-39 molecular sieve catalysts.Take Na-SSZ- 39 molecular sieve 10g are placed in the ammonium nitrate solution that 500ml concentration is 1.0M, after 80 DEG C of oil bath 12h, distilled water washing and filtering, 110 DEG C dry 12h, repeat above step and obtain NH4- SSZ-39 molecular sieves.By 5g NH4- SSZ-39 molecular sieves are placed in concentration The Cu (CH3COO) of 0.15M2In the aqueous solution, after 80 DEG C of oil bath 12h, distilled water washing and filtering, 110 DEG C dry 12h, after 550 DEG C of roasting temperature 4h, repeat above step and obtain Cu-SSZ-39 molecular sieves 2 times.
In the present invention, the evaluation of catalyst is adopted with the following method：
By 2g Cu-SSZ-39 catalyst fineses, 2g mass fractions are that 30% Ludox mixes with 5g water, prepare slurries, Cordierite honeycomb ceramic matrix sample is coated on, catalyst coated weight is about 250gL-1, sample in 100 DEG C of dryings 2 hours, 500 DEG C are calcined 2 hours, the monoblock type Cu-SSZ-39 catalyst for as preparing, in putting it into fixed bed activity rating device, Simulated flue gas composition is 1000ppm NO, 1100ppm NH3, 5%O2And 10%H2O, reaction velocity is 30,000h-1。
The Cu-SSZ-39 catalyst lab scale samples that will be coated on cordierite are placed in tube furnace, in containing water vapor quality Fraction be 10% air stream (flow is 200L/h) in aging 12h at 600~800 DEG C, obtain aged samples.
Accompanying drawing 1 is one-step method double template, and ion-exchange and infusion process prepare the XRD of Cu-SSZ-39, as seen from the figure One-step method and two-step method successfully synthesize the SSZ-39 crystal formations of AEI structures.
Accompanying drawing 2 is one-step method double template, and ion-exchange and infusion process prepare the XRD of the aged samples of Cu-SSZ-39 Figure, it is seen that 800 degrees Celsius of aging rear Cu-SSZ-39 remain in that complete AEI structures, crystallinity slightly has compared with fresh sample Decline.
Accompanying drawing 3 is the SEM figures of one-step method double template synthesis Cu-SSZ-39, and it has regular cubic.
Attached Figure 4 and 5 are fresh and aged samples the NO conversion ratio figures of Cu-SSZ-39 prepared by three kinds of methods, by two figures pair Than visible, the Cu-SSZ-39 phases that Cu-SSZ-39 prepared by one-step method double template is prepared with two-step ion exchange and infusion process Difference is little, is respectively provided with excellent fresh and aging activity.So as to the technique for further embodying one-step method double template preparation method Simply, the advantage such as environmental protection.
Applicant states, person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, to the present invention The addition of the equivalence replacement and auxiliary element of each raw material of product, selection of concrete mode etc., all fall within protection scope of the present invention Within the scope of disclosure.

Claims (6)

1. a kind of preparation method with double template one-step synthesis method Cu-SSZ-39 molecular sieve catalysts, comprises the following steps：
(1) USY molecular sieve is prepared：By business NH4- Y zeolites dealuminzation under 700 DEG C of vapor, after at 75 DEG C, the sulfuric acid of 0.74M is molten Processed 4 hours in liquid, obtain the silicon source and silicon source USY molecular sieve as synthesis Cu-SSZ-39 molecular sieve catalysts；
(2) using as the USY molecular sieve of silicon source and silicon source, NaOH, copper sulphate, TEPA and organic formwork agent successively Primogel is obtained after being sufficiently stirred in addition deionized water；The organic formwork agent is tetraethyl hydroxide phosphine, tetraethyl hydrogen Any one in amine-oxides and N, N- diisopropylethylamine；Each reaction raw materials as silicon source and silicon source USY molecular sieve, two The addition of silica, aluminum oxide, copper sulphate-TEPA, You Jimo, sodium oxide molybdena, water and template, successively according to mole Than being 1.0：0.1~1.0：0~1.0：0.2~2.0：0.1~0.5：20~50 are fed intake；
(3) complete gel will be stirred to be placed in hydrothermal reaction kettle, crystallization 1~7 day, is cooled to room temperature at 150~180 DEG C, Through centrifugal filtration, deionized water washing, dry, calcined at 500~850 DEG C, obtain Cu-SSZ-39.
2. preparation method according to claim 1, it is characterised in that obtained Cu-SSZ-39 molecular sieve catalysts Silica alumina ratio is 4.5~16.4.
3. preparation method according to claim 1, it is characterised in that obtained Cu-SSZ-39 molecular sieve catalysts Copper load capacity is 2.00~5.00wt.%.
4. the Cu-SSZ-39 molecular sieve catalysts that the preparation method described in claim 1,2 or 3 is prepared are in exhaust gas from diesel vehicle Application in cleaning system.
5. application according to claim 4, it is characterised in that the described application tool in diesel car tail gas refining system Body is for oxynitrides SCR (NH in exhaust gas from diesel vehicle3- SCR) process.
6. application according to claim 7, it is characterised in that the described application tool in diesel car tail gas refining system Body is to eliminate NO for selective catalysis.
CN201710099479.2A 2017-02-23 2017-02-23 The preparation method and applications of the molecular sieve catalysts of one-step synthesis method Cu SSZ 39 Pending CN106799255A (en)

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CN113797965A (en) * 2020-06-17 2021-12-17 中国科学院大连化学物理研究所 Preparation method of titanium silicalite molecular sieve crystal-loaded copper nanoparticle catalyst
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