CN109126862A - It is a kind of accelerate synthesis CHA structure molecular sieve method and its catalyst NH3-SCR reaction in application - Google Patents

It is a kind of accelerate synthesis CHA structure molecular sieve method and its catalyst NH3-SCR reaction in application Download PDF

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CN109126862A
CN109126862A CN201810948803.8A CN201810948803A CN109126862A CN 109126862 A CN109126862 A CN 109126862A CN 201810948803 A CN201810948803 A CN 201810948803A CN 109126862 A CN109126862 A CN 109126862A
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molecular sieve
cha structure
promotor
structure molecular
solution
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李凯祥
李振国
任晓宁
邵元凯
刘双喜
高继东
吴撼明
钟祥麟
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China Automotive Technology and Research Center Co Ltd
CATARC Tianjin Automotive Engineering Research Institute Co Ltd
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China Automotive Technology and Research Center Co Ltd
CATARC Tianjin Automotive Engineering Research Institute Co Ltd
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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
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • 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
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/783—CHA-type, e.g. Chabazite, LZ-218
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
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    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2255/00—Catalysts
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    • B01D2255/2065—Cerium
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    • B01D2255/2073—Manganese
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    • B01D2255/20738—Iron
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    • B01D2255/20—Metals or compounds thereof
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    • B01D2255/20761—Copper
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2255/207—Transition metals
    • B01D2255/20769—Molybdenum
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites

Abstract

A kind of promotor of quickening synthesis CHA structure molecular sieve of the invention effectively shortens the synthesis cycle of molecular sieve, and the hydrothermal synthesis time foreshortens to 20-24h；And using above-mentioned CHA structure molecular sieve as carrier, CHA structure molecular screen base SCR catalyst is prepared by quick negative pressure impregnation method, is uniformly dispersed, without the miscellaneous peak other than CHA structure in XRD spectra；NH is carried out using simulated atmosphere on self assembly micro fixed-bed reactor3- SCR performance evaluation, operation temperature window T90(T90, NOXTemperature when conversion ratio 90%) it is 180-475 DEG C, N295% or more selectivity, average NH3Leakage rate is lower than 10ppm.

Description

It is a kind of accelerate synthesis CHA structure molecular sieve method and its catalyst in NH3- SCR is anti- Application in answering
Technical field
The invention belongs to Vehicular exhaust nitrogen oxides Catalytic Reducing Purification (SCR, Selective Catalytic Reduction) technical field, a kind of fast preparation method more particularly, to CHA structure molecular sieve and leads on this basis The method for crossing quick negative pressure impregnation preparation SCR catalyst.
Background technique
With the fast development of Domestic Automotive Industry, vehicle guaranteeding organic quantity increases year by year, and 2017 end of the year whole nations of cut-off are motor-driven Vehicle ownership is more than 3.10 hundred million amounts, wherein 2.17 hundred million, automobile.The comprehensively universal of motor vehicle significantly improves going out for people It goes, but has also caused a series of problems, especially pollution emission problem.According to Environmental Protection Department " Chinese automotive environment pipe Manage annual report (2017) ", national 3419.3 ten thousand tons of motor vehicle emission pollutant carbon monoxide (CO) in 2016, hydrocarbon (HC) 422.0 ten thousand tons, nitrogen oxides (NOX) 577.8 ten thousand tons, 53.4 ten thousand tons of particulate matter (PM).By fuel grade, national emission of diesel engine NOX70%, PM of accounting vehicle mass exhaust total quantity is then more than 90%.Therefore, exhaust gas from diesel vehicle already becomes China's atmosphere pollution One of major source.Wherein, NOXAs one of four kinds of major pollutants, photochemical fog, acid rain, haze etc. can be caused A series of atmosphere pollution phenomenons, seriously threaten natural environment and human health.Solve vehicle exhaust NOXPollute very urgent, mesh Preceding SCR technology (Selective Catalytic Reduction, SCR) is most effective most widely used skill Art.By way of additional reducing agent, under the effect of the catalyst, by NOXIt is converted to N2。
State four, five stages most widely used vanadium system SCR catalyst, due to poor performance at low temperatures, nitrogen selective it is low and Vanadium secondary pollution problems can not be applicable in six discharge phase of state that will implement.And molecular screen base SCR catalyst will be as future Trend has become research hotspot.CHA structure molecular sieve possesses high silica alumina ratio and small duct, frequently as the load of SCR catalyst Body, corresponding molecular sieve catalyst have good De-NOXPerformance.Wherein, SAPO-34, SSZ-13 are automotive catalyst fields The most common CHA structure molecular sieve carrier.Usual CHA structure molecular sieve preparation method is by silicon source, silicon source, template, alkali metal Element etc., which sequentially adds, is prepared into complex sol, is subsequently placed in high temperature crystallizing kettle, and hydrothermal synthesis reaction is carried out under static condition, Form molecular sieve product.This method lacks the inducer of crystal growth, and formation nucleus is slower, leads to the entire hydrothermal synthesis period It is longer, CHA structure molecular sieve water heat generated time is synthesized in 106927474 A of patent CN to be no less than 4 days；Patent CN CHA structure zeolite-water thermal synthesis duration 3-8 days in 107115888 A；CHA structure molecular sieve in 107282096 A of patent CN A length of 3-7 days when hydrothermal synthesis；CHA structure zeolite-water thermal synthesis duration is 4-5 days in 106745034 A of patent CN.Separately Outside, conventional molecular sieve hydrothermal synthesis is in static condition, for example 106745035 A of 106986354 A of patent CN and CN, in this way The advantages of doing is to be conducive to molecular sieve growth, the disadvantage is that molecular sieve particle diameter distribution is uneven, moieties sieve size particle is larger, very To there is caking phenomenon.
Under normal circumstances, molecular sieve SCR catalyst preparation method can be divided into infusion process and ion-exchange, and above method is negative It carries active component and is required to drying later, often because capillary occurs for solution surface tension in duct in Jie's poromerics drying process Coacervation causes Active components distribution uneven.In order to avoid the phenomenon, the present invention uses quick negative pressure impregnation method, using grinding Mill processing, refines catalyst carrier particle, selects the organic matter of low boiling point low-tension as solvent, in the way of vacuum distillation Obtain catalyst precarsor.
Summary of the invention
It is a kind of accelerate synthesis of molecular sieve method and its catalyst NH3-SCR reaction in application, it is following for solving Problem: 1) Zeolite synthesis excessive cycle；2) catalyst activity component is unevenly distributed.
In order to solve the above technical problems, the invention the technical solution adopted is that:
A kind of promotor for accelerating synthesis CHA structure molecular sieve, the promotor is by inorganic compound promotor, organic compound Object promotor and CHA structure molecular screen primary powder composition, inorganic compound promotor: organic compound promotor molar ratio is 1: 0.1-25, CHA structure molecular screen primary powder additional amount are every hundred milliliters of solution 0.01-0.5g.
Wherein, inorganic compound promotor is at least one in fluoride, nitrate, alkali metal salt or alkali salt Kind, fluoride can be NH4F, one of HF, nitrate can be NH4NO3、KNO3、NaNO3、LiNO3、Mg(NO3)2In One kind, alkali metal salt can be NaCl, Na2SO4、Na3PO4、KCl、K2SO4、K3PO4、KH2PO4One of, alkali salt It can be MgCl2、MgSO4One of.
Wherein, organic compound promotor be tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, At least one of etamon chloride, triethylamine, diethylamine.
Wherein, the CHA structure molecular screen primary powder is one of SAPO-34, SSZ-13.
In addition, the present invention also resides in a kind of method for accelerating synthesis CHA structure molecular sieve with above-mentioned promotor that discloses, including Following key step:
S1: one of sodium metaaluminate, Aluminum sol or aluminum nitrate are configured to Crystallization of Zeolite liquid, the Crystallization of Zeolite Liquid, inorganic compound promotor, organic compound promotor and CHA structure molecular screen primary powder are proportionally mixed to form compound molten Glue-gel.
S2: complex sol-gel in S1 is placed in reaction vessel, and synthesizes CHA structure molecule with hydrothermal synthesis method Sieve precursor carrier；
S3: the molecular sieve carrier precursor in S2 is successively centrifuged, is washed, is dried, roasts and obtains CHA structure molecular sieve Carrier.
Wherein, the molar ratio of promotor and aluminium element is 0.05%~5% in S1；Preferably, promotor and aluminium element Molar ratio is 0.1~2%.
Wherein, the condition of hydrothermal synthesis method uses following ladder temperature control and program mixing control in S2, firstly, 180-200 DEG C stirring reacts 2h；Secondly, 130-160 DEG C of standing 12h；Then, it under 130-160 DEG C of constant temperature, is stirred at interval of 2h Machine crawl 30s；
The hydrothermal synthesis method time is 20-24h.
Wherein, in S3 gained CHA structure molecular sieve carrier in without obvious stray crystal, relative crystallinity reaches 90% or more.
In addition, the present invention, which also resides in disclosure, prepares resulting CHA structure system with molecular sieve for preparing using the above method for SCR catalyst Method, including following key step:
S1:CHA structure molecular screen support dispersion is added in water mixed alkoxide solution, macromolecule dispersing agent is added, by grinding Grinding machine carries out grinding and homogeneous solution is made；
S2: solution with active component element is proportionally added into S1 homogeneous solution and with adjuvant component element Solution is dispersed with stirring uniformly；
S3: S2 solution is placed in rotary evaporation bottle, and the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve Catalyst is made in SCR catalyst precursor, then drying roasting.
Wherein, according to mass ratio, CHA structure molecular sieve carrier: water: alcohol=1:(0.2-0.9): (1-10).
Wherein, the macromolecule dispersing agent in S1 can be (poly- for polyethylene glycol (degree of polymerization 3000-6000), polyethylene glycol Right is 6000-10000), one of polyvinyl alcohol (degree of polymerization 6000-10000).
Wherein, active component element is loaded on the CHA structure molecular screen base in CHA structure molecular screen base SCR catalyst And adjuvant component element, the active component element relative to carrier mass ratio be no more than 6%, the adjuvant component element relative to The mass ratio of carrier is no more than 2.5%.
Wherein, active component element be at least one of copper, ferro element, adjuvant component element be cerium, manganese, iron, molybdenum, At least one of selenium, niobium, lanthanum, praseodymium element.
It is being catalyzed in addition, the present invention also resides in the open CHA structure molecular screen base SCR catalyst obtained using the above method Purify NOXIn application, specifically, in tail gas catalyzed reduction reaction (NH3- SCR) in application.
From molecular sieve crystal nucleation, growth angle is promoted, molecular screen primary powder adds technical solution provided by the invention Enter, reduce the activation energy that nucleus is formed, organic/inorganic compound promotor improves micelle character, promotes nucleus fast-growth.Tool Have the advantage that and the utility model has the advantages that
(1) molecular screen primary powder provides nucleus in promotor, and inorganic compound accelerates nucleus molding, guides Si-O-Al structure It grows and molecular sieves stabilized structure, organic compound improves sol property, acceleration molecular sieve space structure is formed.Three of the above object Texture at promotor, not only accelerate the nucleation and growth of crystal, form crystal quickly, also shorten CHA structure The synthesis cycle of molecular sieve, hydrothermal synthesis time foreshorten to 20-24h；
(2) it using above-mentioned CHA structure molecular sieve as carrier, is catalyzed using the molecular screen base SCR of quick negative pressure impregnation method preparation Agent avoids copper solution in micropore canals and aggregation concentration phenomena occurs since solvent volatilizees rapidly, so active specy dispersion is equal It is even, without the miscellaneous peak other than CHA structure in XRD spectra.
(3) it is carried out on self assembly micro fixed-bed reactor using simulated atmosphere (atmospheric condition is shown in specific embodiment) NH3- SCR performance evaluation, operation temperature window T90(T90, NOXTemperature when conversion ratio 90%) it is 180-475 DEG C, N2Selection Property 95% or more, average NH3Leakage rate is lower than 10ppm.
Detailed description of the invention
Fig. 1 is the XRD spectra of CHA structure molecular sieve prepared by case study on implementation 1；
Fig. 2 is the NH of CHA structure molecular screen base SCR catalyst prepared by case study on implementation 13- SCR reacts NOXConversion ratio is bent Line；
Fig. 3 is the NH of CHA structure molecular screen base SCR catalyst prepared by case study on implementation 13- SCR reacts N2Selectivity curve；
Fig. 4 is the NH of CHA structure molecular screen base SCR catalyst prepared by case study on implementation 13- SCR reacts NH3Reveal curve.
Fig. 5 is the microscopic appearance photo (SEM photograph) of CHA structure molecular sieve prepared by case study on implementation 1；
Fig. 1-Fig. 5 belongs to the result that 40-60 mesh catalyst sample is tested in self assembly micro fixed-bed reactor.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described Experimental method is unless otherwise specified conventional method.
In the present invention, the simulated flue gas group ingredient of use: 500ppm NO, 500ppm NH3, 5%O2, N2For Balance Air, Total flow is 1000ml/min, reaction velocity 30000h-1。
Below in conjunction with embodiment come the present invention will be described in detail create.
Case study on implementation 1
(1) preparation of molecular sieve carrier:
18.2g sodium metaaluminate is weighed first and is configured to Crystallization of Zeolite liquid, and 0.074g ammonium fluoride (NH is added thereto4F) With 0.165g etamon chloride (TEAC) and 0.02g SAPO-34 molecular screen primary powder.It stirs evenly to form complex sol- Gel.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, 180 DEG C of stirrings react 2h； 150 DEG C of standing hydrothermal synthesis 12h；Then, under 150 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times with Afterwards, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting Product is obtained, labeled as 1., Crystal Structure (XRD spectra) is shown in Fig. 1, and product occurs belonging to CHA knot as we know from the figure The characteristic diffraction peak of structure molecular sieve illustrates molecular sieve for CHA structure.SEM photograph is shown in Fig. 5, and CHA structure point is presented in product Son sieves unique cube pattern.Its relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added to 30ml ethanol-water solution (water alcohol ratio is 45%) mixing molten It in liquid, is added 2ml polyethylene glycol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；Xiang Jun The copper nitrate solution of 2ml 49.8% is added in even solution, 0.03g cerous nitrate and 0.16g lanthanum nitrate is added as auxiliary agent, stirring It is uniformly dispersed；Solution is placed in rotary evaporation bottle, the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR and urges Agent precursor, then drying roasting catalyst is made, labeled as 1. -1., be catalyzed NOXThe T of conversion50(when conversion ratio is 50% Temperature), temperature window T90(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2, corresponding NOXConversion Rate, N2Selectivity and NH3Amount of leakage curve is shown in Fig. 2,3,4 respectively.Fig. 2 shows the operation temperature window T of the catalyst90For 188- 475 DEG C, N2Selectivity is more than 92%, average NH3Amount of leakage is in 10ppm or less.
Case study on implementation 2
(1) preparation of molecular sieve carrier:
100g Aluminum sol (25% solid content, acid) is weighed first and is configured to Crystallization of Zeolite liquid, and 0.25g is added thereto Potassium nitrate (KNO3) and 0.075g triethylamine (TEA) and 0.02g SAPO-34 molecular screen primary powder.Stir evenly to be formed it is compound Sol-gel.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, 180 DEG C of stirrings react 2h； 150 DEG C of standing hydrothermal synthesis 12h；Then, under 150 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times with Afterwards, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting CHA structure molecular sieve is obtained, labeled as 2., relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added in 30ml methanol-water (water alcohol ratio is 45%) mixed solution, It is added 2ml polyethylene glycol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；To homogeneous solution The middle copper nitrate solution that 2ml 49.8% is added is added 0.05g cerous nitrate and 0.05g manganese nitrate as auxiliary agent, is dispersed with stirring It is even；Solution is placed in rotary evaporation bottle, the Organic Alcohol in solution is evaporated in vacuo, before obtaining half-dried molecular sieve SCR catalyst Body, then drying roasting catalyst is made, labeled as 2. -2., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50% Degree), temperature window T90(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Case study on implementation 3
(1) preparation of molecular sieve carrier:
375.13g aluminum nitrate is weighed first and is configured to Crystallization of Zeolite liquid, and 4.2g potassium phosphate (K is added thereto3PO4) and 0.026g tetrabutylammonium hydroxide (TBAH) and 0.02g SAPO-34 molecular screen primary powder.It stirs evenly to form complex sol- Gel.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, 180 DEG C of stirrings react 2h； 150 DEG C of standing hydrothermal synthesis 12h；Then, under 150 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times with Afterwards, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting CHA structure molecular sieve is obtained, labeled as 4., relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added to 30ml ethylene glycol-water (water alcohol ratio is 45%) mixed solution In, it is added 2ml polyethylene glycol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；To uniform The copper nitrate solution of 2ml 49.8% is added in solution, 0.2g cerous nitrate is added as auxiliary agent, is dispersed with stirring uniformly；Solution is set In rotary evaporation bottle, the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR catalyst precursor, then dries Roasting catalyst is made, labeled as 4. -4., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%), temperature window T90 (temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Case study on implementation 4
(1) preparation of molecular sieve carrier:
18.2g sodium metaaluminate is weighed first and is configured to Crystallization of Zeolite liquid, and 0.085g ammonium fluoride is added thereto (NaNO3), 0.02g dipotassium hydrogen phosphate (K2HPO4) and 0.065g etamon chloride (TEAC) and 0.02g SAPO-34 points Son sieve original powder.It stirs evenly to form complex sol-gel.
Hydrothermal synthesis step such as embodiment 1 is identical, and gained molecular sieve carrier number is that 5., relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added in 30ml acetone-water (volumetric concentration 45%) mixed solution, It is added 2ml polyvinyl alcohol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；To homogeneous solution The middle copper nitrate solution that 2ml 49.8% is added is added 0.13g nitric acid niobium and 0.06g nitric acid molybdenum as auxiliary agent, is dispersed with stirring It is even；Solution is placed in rotary evaporation bottle, the Organic Alcohol in solution is evaporated in vacuo, before obtaining half-dried molecular sieve SCR catalyst Body, then drying roasting catalyst is made, labeled as 5. -5., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50% Degree), temperature window T90(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Case study on implementation 6
(1) preparation of molecular sieve carrier:
CHA structure molecular sieve feed ratio is same as Example 5.
Complex sol-gel of preparation is placed in magnetic coupling mechanic whirl-nett reaction kettle, 200 DEG C of stirring reactions 2h；155 DEG C of standing hydrothermal synthesis 12h；Then, under 155 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times After, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting Burning obtains CHA structure molecular sieve, and for products obtained therefrom labeled as 6., relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
The molecular sieve dispersion for taking 10g made above is added in 30ml water alcohol (water alcohol ratio is 45%) mixed solution, is added 2ml polyvinyl alcohol (degree of polymerization 6000-10000) carries out grinding by grinder and homogeneous solution is made；Add into homogeneous solution Enter the copper nitrate solution of 2ml 49.8%, 0.05g ferric nitrate and 0.05g cerous nitrate is added as auxiliary agent, is dispersed with stirring uniformly；It will Solution is placed in rotary evaporation bottle, and the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR catalyst precursor, with Afterwards drying roasting catalyst is made, labeled as 6. -6., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%), temperature Window T90(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Case study on implementation 7
(1) preparation of molecular sieve carrier:
CHA structure molecular sieve feed ratio and molecular sieve water heat synthesis step are identical as case study on implementation 5.Obtain CHA structure point Son sieve, labeled as 7., relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
The molecular sieve dispersion for taking 10g made above is added to 30ml methanol/ethylene glycol (molar ratio 3:1) mixed solution In, it is added 2ml polyethylene glycol (degree of polymerization 3000-6000), carries out grinding by grinder and homogeneous solution is made；To uniformly it is molten The copper nitrate solution of 2ml 49.8% is added in liquid, 0.1g manganese nitrate and 0.1g ferric nitrate is added as auxiliary agent, is dispersed with stirring It is even；Solution is placed in rotary evaporation bottle, the Organic Alcohol in solution is evaporated in vacuo, before obtaining half-dried molecular sieve SCR catalyst Body, then drying roasting catalyst is made, labeled as 7. -7., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50% Degree), temperature window T90(temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Comparative example 1
(1) preparation of molecular sieve carrier:
82g sodium metaaluminate is weighed first and is configured to Crystallization of Zeolite liquid, does not add promotor and crystal seed.It stirs evenly to be formed Complex sol-gel.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, 180 DEG C of stirrings react 2h； 150 DEG C of standing hydrothermal synthesis 12h；Then, under 150 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times with Afterwards, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting CHA structure molecular sieve is obtained, 1. labeled as DB-, relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added in 30ml ethanol water (water alcohol ratio is 45%) mixed solution, It is added 2ml polyethylene glycol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；To homogeneous solution The middle copper nitrate solution that 2ml 49.8% is added, is added 0.1g cerous nitrate, is dispersed with stirring uniformly；Solution is placed in rotary evaporation bottle In, the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR catalyst precursor, catalysis is made in then drying roasting Agent, labeled as DB- 1. -1., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%), temperature window T90(conversion ratio >= Temperature range when 90%) and N2Selective data is shown in Table 2.
Comparative example 2
(1) preparation of molecular sieve carrier:
82g sodium metaaluminate is weighed first and is configured to Crystallization of Zeolite liquid, and 0.5g potassium nitrate (KNO is added thereto3) and 0.1g tetraethyl ammonium hydroxide (TEAH) and 0.02g SAPO-34 molecular screen primary powder.Stir evenly that form complex sol-solidifying Glue.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, thermostatted water under 155 DEG C of static conditions Thermal response is for 24 hours.CHA structure molecular sieve is obtained, 2. labeled as DB-, relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
Above-mentioned 10g CHA structure molecular sieve dispersion is taken to be added in 30ml alcohol-water (water alcohol ratio is 45%) mixed solution, It is added 2ml polyethylene glycol (degree of polymerization 6000-10000), carries out grinding by grinder and homogeneous solution is made；To homogeneous solution The middle copper nitrate solution that 2ml 49.8% is added is added 0.1 cerous nitrate as auxiliary agent, is dispersed with stirring uniformly；Solution is placed in rotation Turn in evaporative flask, the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR catalyst precursor, then drying roasting Catalyst is made, labeled as DB- 2. -2., be catalyzed NOXThe T of conversion50(temperature when conversion ratio is 50%), temperature window T90 (temperature range when conversion ratio >=90%) and N2Selective data is shown in Table 2.
Comparative example 3
(1) preparation of molecular sieve carrier:
Weigh 82g sodium metaaluminate first and be configured to Crystallization of Zeolite liquid, thereto be added 0.5g potassium nitrate (KNO3) and 0.1g tetraethyl ammonium hydroxide (TEAH) and 0.02g SAPO-34 molecular screen primary powder.Stir evenly that form complex sol-solidifying Glue.
Above-mentioned complex sol-gel is placed in magnetic coupling mechanic whirl-nett reaction kettle, 180 DEG C of stirrings react 2h； 150 DEG C of standing hydrothermal synthesis 12h；Then, under 150 DEG C of constant temperatures, at interval of 2h crawl blender；Blender crawl 3 times with Afterwards, constant temperature stands hydrothermal synthesis 4h.After hydrothermal synthesis, molecular sieve precursor is successively centrifuged, washs, dry, roasting CHA structure molecular sieve is obtained, 3. labeled as DB-, relative crystallinity is shown in Table 1.
(2) preparation of molecular sieve SCR catalyst:
0.1g nitre is added using traditional infusion process, the copper nitrate solution of 2ml 49.8% in the molecular sieve for taking 10g made above For sour cerium as auxiliary agent, forced air drying obtains molecular sieve SCR catalyst precursor, and catalyst is made in then drying roasting, is labeled as DB- 3. 3. catalysis NOXThe T of conversion50(temperature when conversion ratio is 50%), temperature window T90(temperature when conversion ratio >=90% Range) and N2Selective data is shown in Table 2.
The different CHA structure molecular sieve relative crystallinity indexs of table 1
Verify embodiment
CHA structure molecular sieve catalyst screening prepared by the embodiment of the present invention 1~7 and comparative example 1~3 is prepared into 40- 60 mesh powder samples, carry out NH on the micro fixed-bed reactor of laboratory self assembly3- SCR catalytic performance test.It uses Crystal reaction tube having a size of 15mm, loaded catalyst 2ml or so.Using simulated flue gas, composition are as follows: 500ppm NO, 500ppm NH3, 5%O2, N2For Balance Air, total flow 1000ml/min, reaction velocity 30000h-1.Catalytic performance index T50、T90The results are shown in Table 2.
The different CHA structure molecular sieve catalyst NH of table 23- SCR performance indicator
Sample is obvious T50 T90
①-① 156℃ 188-475℃
②-② 153℃ 175-470℃
③-③ 150℃ 190-475℃
④-④ 149℃ 185-470℃
⑤-⑤ 155℃ 180-480℃
⑥-⑤ 148℃ 176-465℃
⑦-⑦ 146℃ 175-467℃
DB-①-① 220℃ 260-355℃
DB-②-② 213℃ 250-400℃
DB-③-③ 175℃ 200-455℃
Above an embodiment of the invention is described in detail, but the content is only the invention Preferred embodiment should not be considered as limiting the invention the practical range of creation.It is all to be made according to the invention application range All the changes and improvements etc., shall remain within the patent scope covered by the invention.

Claims (10)

1. a kind of promotor for accelerating synthesis CHA structure molecular sieve, which is characterized in that the promotor is promoted by inorganic compound Agent, organic compound promotor and CHA structure molecular screen primary powder composition, inorganic compound promotor: organic compound promotor Molar ratio is 1:0.1-25, and CHA structure molecular screen primary powder additional amount is every hundred milliliters of solution 0.01-0.5g.
2. a kind of promotor for accelerating synthesis CHA structure molecular sieve according to claim 1, which is characterized in that inorganization Closing object promotor is at least one of fluoride, nitrate, alkali metal salt or alkali salt.
3. a kind of promotor for accelerating synthesis CHA structure molecular sieve according to claim 1, which is characterized in that organise Conjunction object promotor be tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etamon chloride, triethylamine, At least one of diethylamine.
4. a kind of promotor for accelerating synthesis CHA structure molecular sieve according to claim 1, which is characterized in that the CHA Structure molecular screen original powder is one of SAPO-34, SSZ-13.
5. a kind of method that promotor using as described in claim 1-4 is any accelerates synthesis CHA structure molecular sieve, feature It is, including following key step:
S1: Crystallization of Zeolite liquid, inorganic compound promotor, organic compound promotor and CHA structure molecular screen primary powder are pressed Complex sol-gel is mixed to form according to ratio.
S2: complex sol-gel in S1 is placed in reaction vessel, and molecular sieve supported with hydrothermal synthesis method synthesis CHA structure Body precursor；
S3: the molecular sieve carrier precursor in S2 is successively centrifuged, is washed, is dried, roasts that obtain CHA structure molecular sieve supported Body.
6. according to the method described in claim 5, it is characterized in that, the condition of hydrothermal synthesis method uses following ladder temperature control in S2 With program mixing control, firstly, 180-200 DEG C of stirring reacts 2h；Secondly, 130-160 DEG C of standing 12h；Then, 130- Under 160 DEG C of constant temperatures, at interval of 2h blender crawl 30s；
The hydrothermal synthesis method time is 20-24h.
7. preparation method of the resulting CHA structure system with molecular sieve for preparing for SCR catalyst, feature using claim 5 the method It is, including following key step:
S1:CHA structure molecular screen support dispersion is added in water mixed alkoxide solution, macromolecule dispersing agent is added, by grinder It carries out grinding and homogeneous solution is made；
S2: solution with active component element is proportionally added into S1 homogeneous solution and with the molten of adjuvant component element Liquid is dispersed with stirring uniformly；
S3: S2 solution is placed in rotary evaporation bottle, and the Organic Alcohol in solution is evaporated in vacuo, obtains half-dried molecular sieve SCR and urges Catalyst is made in agent precursor, then drying roasting.
8. according to the method described in claim 7, it is characterized by: CHA structure in CHA structure molecular screen base SCR catalyst Active component element and adjuvant component element are loaded on molecular screen base, the active component element relative to carrier mass ratio not More than 6%, which is no more than 2.5% relative to the mass ratio of carrier.
9. according to the method described in claim 8, it is characterized in that, active component element be at least one of copper, ferro element, Adjuvant component element is at least one of cerium, manganese, iron, molybdenum, selenium, niobium, lanthanum, praseodymium element.
10. the CHA structure molecular screen base SCR catalyst obtained according to 7 the method for right is in catalytic purification NOXIn application.
CN201810948803.8A 2018-08-20 2018-08-20 It is a kind of accelerate synthesis CHA structure molecular sieve method and its catalyst NH3-SCR reaction in application Pending CN109126862A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111203269A (en) * 2020-04-21 2020-05-29 稀土催化创新研究院(东营)有限公司 Multi-metal-CHA type molecular sieve catalyst and preparation method and application thereof
CN111924857A (en) * 2020-08-26 2020-11-13 威海太平洋新材料有限公司 Synthesis method of spherical SSZ-13 molecular sieve
CN112156808A (en) * 2020-09-30 2021-01-01 中汽研（天津）汽车工程研究院有限公司 Preparation method and application of molecular sieve SCR catalyst with low ammonia escape rate
CN112473730A (en) * 2020-12-14 2021-03-12 大连海事大学 Copper-based CHA-type silicon-aluminum molecular sieve catalyst and preparation method thereof
CN112604710A (en) * 2020-12-10 2021-04-06 大连理工大学盘锦产业技术研究院 Novel efficient denitration catalyst and preparation method and application thereof
CN113856749A (en) * 2021-08-26 2021-12-31 中汽研（天津）汽车工程研究院有限公司 Samarium-based CHA molecular sieve catalyst and application thereof
CN115532253A (en) * 2022-09-28 2022-12-30 中国汽车技术研究中心有限公司 Internal combustion engine tail gas purification catalyst and preparation method thereof

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121529A (en) * 2006-08-08 2008-02-13 中国科学院大连化学物理研究所 Fast synthetic method for phosphorus-silicon-aluminum molecular sieve
US7442365B1 (en) * 2004-06-14 2008-10-28 Uop Llc Process for preparing molecular sieve beads
CN101462742A (en) * 2009-01-14 2009-06-24 南开大学 Preparation of fine grain SAPO-34 molecular sieve
CN101668589A (en) * 2007-02-27 2010-03-10 巴斯福催化剂公司 copper cha zeolite catalysts
CN101674885A (en) * 2007-03-26 2010-03-17 Pq公司 Comprise and have 8 yuan of ring molecular sieves of open-celled structures or novel microporous crystalline material of zeolite and its production and application
CN101983103A (en) * 2008-01-31 2011-03-02 巴斯夫公司 Catalysts, systems and methods utilizing non-zeolitic metal-containing molecular sieves having the cha crystal structure
CN103298557A (en) * 2010-12-02 2013-09-11 庄信万丰股份有限公司 Zeolite catalyst containing metal
CN103764282A (en) * 2011-07-27 2014-04-30 庄信万丰股份有限公司 Low phosphorus chabazites
CN104229829A (en) * 2013-06-17 2014-12-24 中国石油化工股份有限公司 Preparation method of small grain SAPO-34 molecular sieve
CN104307564A (en) * 2014-09-09 2015-01-28 天津大学 Auxiliary agent doped Cu-SAPO-34 catalyst, preparation method and applications thereof
CN105439171A (en) * 2015-12-22 2016-03-30 天津众智科技有限公司 Method for preparing SAPO-34 molecular sieve by using carbonate as synthesis prompting agent, and applications thereof
CN105692647A (en) * 2016-03-17 2016-06-22 山东齐鲁华信高科有限公司 Preparation method of SSZ-13 molecular sieve
CN106622227A (en) * 2016-12-29 2017-05-10 天津大学 Preparation method of monoatomic catalyst for indoor air purification

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7442365B1 (en) * 2004-06-14 2008-10-28 Uop Llc Process for preparing molecular sieve beads
CN101121529A (en) * 2006-08-08 2008-02-13 中国科学院大连化学物理研究所 Fast synthetic method for phosphorus-silicon-aluminum molecular sieve
CN101668589A (en) * 2007-02-27 2010-03-10 巴斯福催化剂公司 copper cha zeolite catalysts
CN101674885A (en) * 2007-03-26 2010-03-17 Pq公司 Comprise and have 8 yuan of ring molecular sieves of open-celled structures or novel microporous crystalline material of zeolite and its production and application
CN101983103A (en) * 2008-01-31 2011-03-02 巴斯夫公司 Catalysts, systems and methods utilizing non-zeolitic metal-containing molecular sieves having the cha crystal structure
CN101462742A (en) * 2009-01-14 2009-06-24 南开大学 Preparation of fine grain SAPO-34 molecular sieve
CN103298557A (en) * 2010-12-02 2013-09-11 庄信万丰股份有限公司 Zeolite catalyst containing metal
CN103764282A (en) * 2011-07-27 2014-04-30 庄信万丰股份有限公司 Low phosphorus chabazites
CN104229829A (en) * 2013-06-17 2014-12-24 中国石油化工股份有限公司 Preparation method of small grain SAPO-34 molecular sieve
CN104307564A (en) * 2014-09-09 2015-01-28 天津大学 Auxiliary agent doped Cu-SAPO-34 catalyst, preparation method and applications thereof
CN105439171A (en) * 2015-12-22 2016-03-30 天津众智科技有限公司 Method for preparing SAPO-34 molecular sieve by using carbonate as synthesis prompting agent, and applications thereof
CN105692647A (en) * 2016-03-17 2016-06-22 山东齐鲁华信高科有限公司 Preparation method of SSZ-13 molecular sieve
CN106622227A (en) * 2016-12-29 2017-05-10 天津大学 Preparation method of monoatomic catalyst for indoor air purification

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GI TAE PARK ET.AL: "Synthesis and Structural Characterization of a CHA-type AlPO4", 《INORGANIC CHEMISTRY》 *
于力娜等: ""低温高活性De-NOx分子筛催化剂的制备及其性能研究"", 《汽车工艺与材料》 *
刘红星等: "用氟化氢-三乙胺复合模板剂合成SAPO-34分子筛的晶化历程", 《催化学报》 *
高滋等: "《沸石催化与分离技术》", 30 November 1999, 中国石化出版社 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111203269A (en) * 2020-04-21 2020-05-29 稀土催化创新研究院(东营)有限公司 Multi-metal-CHA type molecular sieve catalyst and preparation method and application thereof
CN111924857A (en) * 2020-08-26 2020-11-13 威海太平洋新材料有限公司 Synthesis method of spherical SSZ-13 molecular sieve
CN112156808A (en) * 2020-09-30 2021-01-01 中汽研（天津）汽车工程研究院有限公司 Preparation method and application of molecular sieve SCR catalyst with low ammonia escape rate
CN112604710A (en) * 2020-12-10 2021-04-06 大连理工大学盘锦产业技术研究院 Novel efficient denitration catalyst and preparation method and application thereof
CN112473730A (en) * 2020-12-14 2021-03-12 大连海事大学 Copper-based CHA-type silicon-aluminum molecular sieve catalyst and preparation method thereof
CN112473730B (en) * 2020-12-14 2024-01-19 大连海事大学 Copper-based CHA type silicon-aluminum molecular sieve catalyst and preparation method thereof
CN113856749A (en) * 2021-08-26 2021-12-31 中汽研（天津）汽车工程研究院有限公司 Samarium-based CHA molecular sieve catalyst and application thereof
CN113856749B (en) * 2021-08-26 2023-10-27 中汽研汽车检验中心（天津）有限公司 Samarium-based CHA molecular sieve catalyst and application thereof
CN115532253A (en) * 2022-09-28 2022-12-30 中国汽车技术研究中心有限公司 Internal combustion engine tail gas purification catalyst and preparation method thereof

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