CN107744830A - The method that one-step method prepares Cu based molecular sieve SCR catalysts - Google Patents
The method that one-step method prepares Cu based molecular sieve SCR catalysts Download PDFInfo
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- CN107744830A CN107744830A CN201711075729.5A CN201711075729A CN107744830A CN 107744830 A CN107744830 A CN 107744830A CN 201711075729 A CN201711075729 A CN 201711075729A CN 107744830 A CN107744830 A CN 107744830A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 59
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 238000005342 ion exchange Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 238000010574 gas phase reaction Methods 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- -1 tetramethyl hydroxide Ammonium Chemical compound 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 241000269350 Anura Species 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229960004643 cupric oxide Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the method that one-step method prepares Cu based molecular sieve SCR catalysts, is characterized in utilizing the molecular sieves of SAPO 34 in the molecular sieve slurry containing template, Cu based molecular sieve SCR catalysts are made by ion exchange.Concretely comprise the following steps：First by the molecular sieve slurry ultrasonic disperse containing template, centrifuging and taking obtains solid, together with copper-containing compound, configure the 1mol/L of copper content 0.1 solution, after adjusting pH, stir and heat carry out ion exchange in solution, be then centrifuged for isolated solid, solid drying and high-temperature roasting are then obtained into Cu based molecular sieve SCR catalysts.It uses the method for ion exchange to be handled the molecular sieve slurry containing template, and by being once calcined to obtain efficient Cu based molecular sieves SCR catalyst, NOx high conversion rate under low temperature environment, whole process is safe, environment-friendly and save energy consumption.
Description
Technical field
The present invention relates to a kind of method that one-step method prepares Cu based molecular sieve SCR catalysts, more particularly to diesel vehicle profit
The preparation method of the Cu based molecular sieve catalyst used in removing NOx is reacted with SCR.
Background technology
Nitrogen oxides (NO, NO2、N2O etc., abbreviation NOx) it is one of main atmosphere pollution, in recent years, country is for ring
The problem of border is polluted is paid attention to further, for diesel vehicle NOxDischarge standard is also increasingly strict.In the diesel engine course of work,
The NO of nitrogen and oxygen reaction generation in air is NOxMain Ingredients and Appearance, therefore NO can not be prevented from sourcexGeneration.Must
Denitration process must be carried out to tail gas, SCR (abbreviation SCR) is processing NOxEffective ways.
According to the difference of reducing agent, the SCR technology being used is divided into Urea-SCR and HC-SCR.Urea-SCR technologies have
Have that catalyst cost is low, and active window is wide, NOxHigh conversion rate, product is pollution-free, ensures the optimal fuel-economy of diesel engine
Property the advantages that, and as the SCR technology of most development potentiality.
SCR catalyst is made up of catalyst and carrier two parts.Wherein cordierite honeycomb structural body is due to its property
Stable, surface area is big, as widely used carrier.Core of the catalyst as SCR system, it is broadly divided into noble metal
Oxide, metal oxide and molecular sieve three major types.What is wherein used now is mostly vanadium titanium catalyst, due to its low-temperature reduction
The shortcomings of difference, V metals have toxicity, and waste catalyst easily causes secondary pollution, it is also necessary to go to solve.But molecular sieve is urged
The advantages that agent is environment-friendly, and temperature window is wide, and heat endurance is strong makes focus of its tool as research.
Molecular sieve catalyst is divided into carried metal and carrier two parts, and common carrier includes ZSM-5, MOR, HBEA, CHA
Deng, wherein the CHA type SAPO zeolite molecular sieves with small structure at 150 DEG C with higher activity, it is and relatively low
N2O selectivity, is adapted to the progress of low-temperature SCR reaction.The same SAPO-34 with CHA types compares with SSZ-13, SAPO-34
Reproducibility is stronger at low temperature, less side products, therefore is more suitable catalyst carrier.Cu has higher as carried metal
Catalytic activity, have broad application prospects.
Molecular sieve slurry containing template needs to be handled just discharge, wherein containing a certain amount of SAPO-34
Molecular sieve is buried and wasted mostly, and the cost for producing SAPO-34 is of a relatively high, and is extracted the molecular sieve in slurry and dropped
The purpose of environmental protection is reached while inexpensive.A kind of micron-level molecular sieve is disclosed in the A patents of CN 103263901 to bear
Carry nanometer copper product preparation method, by liquid phase reduction on molecular sieve carrier in-situ preparation nanometer copper ion.
CN102774850 A patents disclose a kind of fast preparation method of cupric mesoporous-microporous composite molecular sieve, using molecular sieve and nitric acid
Copper solution and Synthesis liquid, hydro-thermal purification synthesis.CN103007998 A patents disclose a kind of nitrous oxide that is used for and are catalytically decomposed
The method prepared with redox molecule sieve catalyst, the exchange of quick copper ion is realized using Ultrasonic Heating.
The above-mentioned method for preparing copper-based molecular sieve catalyst, the raw material costliness used being mostly present, preparation cost is higher,
The condition needed is harsh, it is difficult to realizes industrialized feature.In addition, preparation process is more, the catalyst of generation is difficult with bavin
Turn into the factor for restricting its development on oily car.
The content of the invention
A kind of one-step method is provided and prepares Cu based molecular sieves SCR the invention aims to improve the deficiencies in the prior art
The method of catalyst.
The technical scheme is that：Cu based molecular sieve SCR catalysts are prepared using the molecular sieve slurry containing template,
It is the method using ion exchange, Cu is loaded on SAPO-34 molecular sieves, make use of the molecule reclaimed in discarded preparation liquid
Sieve, the effect recycled is reached.Can Cu by the method for ion exchange2+It is dispersed, so as to obtain higher work
The catalyst of property and conversion ratio, reaches the requirement of practical application.
The present invention concrete technical scheme be：The method that one-step method prepares Cu based molecular sieve SCR catalysts, its feature exist
In：Using the SAPO-34 molecular sieve slurries containing template, by copper by the method for ion exchange in solution with Cu2+Form it is equal
It is even to load on molecular sieve, and the mass fraction of copper reaches 0.4-10.0%, by being once calcined, obtains efficient SCR catalysis
Agent.
Furtherly, the method that one-step method prepares Cu based molecular sieve SCR catalysts, it is comprised the following steps that：
A) deionized water is added into synthesis SAPO-34 molecular sieve kettle liquids, makes quality solid content in 2-15%, ultrasound point
Dissipate, obtain suspension；
B) suspension obtained by step a) is centrifuged, obtains solid；
C) deionized water is added to the solid obtained by step b), obtains the suspension that solid content is 5-15wt%；
D) compound nantokite is weighed, step c) gained suspensions is added, control the content of copper 0.1-1mol/L, stirs,
Obtain suspension；
E) alkali is added into suspension obtained by step d), adjusts pH to 4-6 while stirring；
F) by suspension high-speed stirred obtained by step e) and heat, carry out ion exchange in solution；
G) suspension obtained by step f) is centrifuged；
H) solid obtained by step g) is subjected to dewatered drying, ground, roasting, that is, obtain Cu based molecular sieve SCR catalysts.
Ultrasonic power described in preferred steps (a) is 30-80kHz, ultrasonic time 0.5-3h.Preferred steps (b) and
(g) centrifugation rate described in is 8000-12000r/min, and centrifugation time is 3-30min.
Alkali described in preferred steps (e) is ammoniacal liquor or TMAH.
Stir speed (S.S.) described in preferred steps (f) is 150-350r/min；50-90 DEG C of heating-up temperature, duration
1.5-6 hour.
Drying temperature described in preferred steps (h) is 100-130 DEG C, dries 1-5 hours；Sintering temperature is 400-800
DEG C, roasting time 2-6 hours.
Above-mentioned synthesis SAPO-34 molecular sieve kettle liquids are preferably that hydro-thermal reaction prepares the kettle liquid of SAPO-34 molecular sieves, consolidated
Phase reaction prepares the kettle liquid of SAPO-34 molecular sieves, gas phase reaction prepares the kettle liquid or SAPO-34 molecular sieves of SAPO-34 molecular sieves
The kettle liquid of film production, wherein the template contained.The species of template includes, TMAH, tetraethyl ammonium hydroxide,
One or more in di-n-propylamine or triethylamine.
It is preferred that described compound nantokite is the sulfate of copper, the nitrate of copper, the villaumite of copper, the acetate of copper or copper
Oxide.More preferably：Copper sulphate, copper nitrate, copper chloride, copper acetate and cupric oxide.
Beneficial effect：
This project preparation process is simple, is advantageously implemented large-scale industrial production SCR catalyst, and use and contain mould
Prepared by the molecular sieve slurry of plate agent, cost is relatively low, short preparation period.The catalyst stability being prepared is higher, when can be long
Between use.
Brief description of the drawings
Fig. 1 is the XRD of embodiment 1-6 Cu-SAPO-34 materials after firing；
Fig. 2 is the SEM figures of embodiment 1-5 Cu-SAPO-34 materials after firing；
Fig. 3 is the TPR figures of the Cu-SAPO-34 materials of embodiment 2,4,8,10 after firing；
Fig. 4 is the SCR performance test figures of embodiment 1-4 Cu-SAPO-34 materials after firing.
Embodiment
Embodiment 1：
Take SAPO-34 molecular screen membranes to prepare kettle liquid, configure the molecular sieve slurry containing template that solid content is 2wt%,
Ultrasonic disperse 0.5h is carried out, ultrasonic power 30kHz, 8000r/min rotating speed centrifuge 3min and obtain solid, added into solid
Deionized water, it is configured to 5wt% suspension about 200ml.Add copper nitrate to be made into 0.1mol/L solution and stir, use
Ammoniacal liquor regulation pH is 4.0.Suspension is subjected to heating stirring, stir speed (S.S.) 150r/min, 50 DEG C of heating-up temperature, heat time
1.5 hour.Gained suspension is centrifuged into 3min in 8000r/min rotating speeds, obtained solid carries out dewatered drying, drying temperature
Spend for 100 DEG C, dry 1 hour, be ground to certain particle diameter, high-temperature roasting, sintering temperature is 400 DEG C, roasting time 2 hours.
Embodiment 2：
Thermal response of fetching water prepares SAPO-34 kettle liquids, configures the molecular sieve slurry containing template that solid content is 15wt%,
Ultrasonic disperse 3h is carried out, ultrasonic power 80kHz, 12000r/min rotating speed centrifuge 30min and obtain solid, added into solid
Deionized water, it is configured to 15wt% suspension about 200ml.Add copper nitrate to be made into 1mol/L solution and stir, use
Ammoniacal liquor regulation pH is 4.4.Suspension is subjected to heating stirring, stir speed (S.S.) 350r/min, 90 DEG C of heating-up temperature, heat time
6 hours.Gained suspension is centrifuged into 30min in 12000r/min rotating speeds, obtained solid carries out dewatered drying, drying temperature
Spend for 130 DEG C, dry 5 hours, be ground to certain particle diameter, high-temperature roasting, sintering temperature is 800 DEG C, roasting time 6 hours.
Embodiment 3：
Thermal response of fetching water prepares SAPO-34 kettle liquids, configures the molecular sieve slurry containing template that solid content is 10wt%,
Ultrasonic disperse 2h is carried out, ultrasonic power 50kHz, 10000r/min rotating speed centrifuge 10min and obtain solid, added into solid
Deionized water, it is configured to 10wt% suspension about 200ml.Copper nitrate is added to be made into 0.5mol/L solution and stir,
It is 4.8 with ammoniacal liquor regulation pH.Suspension is subjected to heating stirring, stir speed (S.S.) 150r/min, 50 DEG C of heating-up temperature, during heating
Between 1.5 hours.Gained suspension is centrifuged into 3min in 8000r/min rotating speeds, obtained solid carries out dewatered drying, drying
Temperature is 110 DEG C, is dried 2 hours, is ground to certain particle diameter, high-temperature roasting, and sintering temperature is 550 DEG C, roasting time 4 hours.
Embodiment 4：
Thermal response of fetching water prepares SAPO-34 kettle liquids, configures the molecular sieve slurry containing template that solid content is 10wt%,
Ultrasonic disperse 2h is carried out, ultrasonic power 50kHz, 10000r/min rotating speed centrifuge 30min and obtain solid, added into solid
Deionized water, it is configured to 10wt% suspension about 200ml.Copper nitrate is added to be made into 0.5mol/L solution and stir,
It is 5.2 with ammoniacal liquor regulation pH.Suspension is subjected to heating stirring, stir speed (S.S.) 150r/min, 50 DEG C of heating-up temperature, during heating
Between 1.5 hours.Gained suspension is centrifuged into 10min in 10000r/min rotating speeds, obtained solid carries out dewatered drying, dries
Dry temperature is 110 DEG C, is dried 2 hours, is ground to certain particle diameter, high-temperature roasting, and sintering temperature is 550 DEG C, and roasting time 4 is small
When.
Embodiment 5：
Thermal response of fetching water prepares SAPO-34 kettle liquids, configures the molecular sieve slurry containing template that solid content is 10wt%,
Ultrasonic disperse 2h is carried out, ultrasonic power 50kHz, 10000r/min rotating speed centrifuge 30min and obtain solid, added into solid
Deionized water, it is configured to 10wt% suspension about 200ml.Copper nitrate is added to be made into 0.5mol/L solution and stir,
It is 5.6 with ammoniacal liquor regulation pH.Suspension is subjected to heating stirring, stir speed (S.S.) 150r/min, 50 DEG C of heating-up temperature, during heating
Between 1.5 hours.Gained suspension is centrifuged into 10min in 10000r/min rotating speeds, obtained solid carries out dewatered drying, dries
Dry temperature is 110 DEG C, is dried 2 hours, is ground to certain particle diameter, high-temperature roasting, and sintering temperature is 550 DEG C, and roasting time 4 is small
When.
Embodiment 6：
Thermal response of fetching water prepares SAPO-34 kettle liquids, configures the molecular sieve slurry containing template that solid content is 10wt%,
Ultrasonic disperse 2h is carried out, ultrasonic power 50kHz, 10000r/min rotating speed centrifuge 30min and obtain solid, added into solid
Deionized water, it is configured to 10wt% suspension about 200ml.Copper nitrate is added to be made into 0.5mol/L solution and stir,
It is 6.0 with TMAH regulation pH.Suspension is subjected to heating stirring, stir speed (S.S.) 150r/min, heating-up temperature
50 DEG C, 1.5 hours heat times.Gained suspension is centrifuged into 10min in 10000r/min rotating speeds, obtained solid is carried out
Dewatered drying, drying temperature are 110 DEG C, are dried 2 hours, are ground to certain particle diameter, high-temperature roasting, and sintering temperature is 550 DEG C, roasting
Burn 4 hours time.
Embodiment 7-10：
Take solid phase reaction to prepare SAPO-34 kettle liquids, configure the molecular sieve slurry containing template that solid content is 10wt%,
Ultrasonic disperse 2h is carried out, ultrasonic power 50kHz, 10000r/min rotating speed centrifuge 30min and obtain solid, added into solid
Deionized water, it is configured to 10wt% suspension about 200ml.Copper sulphate, copper acetate, copper chloride and cupric oxide is separately added into be made into
0.5mol/L solution and stir, adjust pH respectively with ammoniacal liquor as 6.0.Suspension is subjected to heating stirring, stir speed (S.S.)
For 150r/min, 50 DEG C of heating-up temperature, 1.5 hours heat times.Gained suspension is centrifuged in 10000r/min rotating speeds
10min, obtained solid carry out dewatered drying, and drying temperature is 110 DEG C, is dried 2 hours, are ground to certain particle diameter, high temperature roasting
Burn, sintering temperature is 550 DEG C, roasting time 4 hours.
Embodiment 11-13：
Take gas phase reaction to prepare SAPO-34 kettle liquids, configure the molecular sieve slurry containing template that solid content is 10wt%,
Ultrasonic disperse 2h is carried out, ultrasonic power 50kHz, 10000r/min rotating speed centrifuge 30min and obtain solid, added into solid
Deionized water, it is configured to 10wt% suspension about 200ml.Add copper nitrate and be made into 0.4,0.6,0.8mol/L solution respectively simultaneously
And stir, pH is adjusted respectively with ammoniacal liquor as 6.0.Suspension is subjected to heating stirring, stir speed (S.S.) 150r/min, heating
Temperature 50 C, 1.5 hours heat times.Gained suspension is centrifuged into 10min, obtained solid in 10000r/min rotating speeds
Dewatered drying is carried out, drying temperature is 110 DEG C, dries 2 hours, is ground to certain particle diameter, high-temperature roasting, sintering temperature 550
DEG C, roasting time 4 hours.
The sample synthesized in embodiment 1-6 is further characterized by XRD, SEM, ICP and BET.
Fig. 1 shows the XRD of embodiment 1-5 Cu-SAPO-34 materials after firing, to confirm the SAPO- after ion exchange
34 structure and crystallinity.
Table 1 shows the ICP and BET of embodiment 1-6 Cu-SAPO-34 materials after firing, after confirming ion exchange
SAPO-34 copper load capacity and microstructure.
Table 1：ICP and BET results under condition of different pH
Table 2 shows the ICP results of embodiment 7-15 Cu-SAPO-34 materials after firing, after confirming ion exchange
SAPO-34 copper load capacity.
Table 2：ICP results under different preparation conditions
| Cu mass fractions (%) | |
| Embodiment 7 | 2.64 |
| Embodiment 8 | 2.34 |
| Embodiment 9 | 2.57 |
| Embodiment 10 | 2.08 |
| Embodiment 11 | 1.27 |
| Embodiment 12 | 6.38 |
| Embodiment 13 | 9.24 |
Fig. 2 shows the SEM of embodiment 1-5 Cu-SAPO-34 materials after firing, to confirm the SAPO- after ion exchange
34 microscopic appearances, above-mentioned chart show that too high pH is not suitable for carrying out ion exchange
The sample synthesized in embodiment 2,4,8,10 detects its reducing property by TPR
Fig. 3 shows the TPR of the Cu-SAPO-34 materials of embodiment 2,4,8,10 after firing, after confirming ion exchange
The ability of SAPO-34 heating schedules reduction consumption hydrogen.By experiment as can be seen that Cu constituent contents are bigger, reducing property is got over
By force.
The sample synthesized in embodiment 4 reduce NOx SCR catalytic test
SCR tests are carried out in the fixed bed quartz tube reactor with 2 cm diameters and 50 centimetre lengths.Experiment is carried out
Between catalyst is granulated into the particles of 0.25-0.42 millimeters.Add in reactor catalysis layer, be heated to 550 DEG C (referring to " table
Reaction condition in 3 ") and kept for 1 hour in a nitrogen atmosphere.Hereafter fed.Use NH3Carry out NO's as reducing agent
SCR.Reaction result is as shown in Figure 4.
The sample synthesized in embodiment 7-13 is tested by SCR, more than more than 80% in 250-350 DEG C of temperature range
Transformation efficiency of the oxides of nitrogen, there is good SCR activity.
Table 3：SCR test conditions
| Total gas flow rate (L/h) | 30 |
| Catalyst loading (mL) | 2 |
| NO concentration (ppm) | 1000 |
| NH3 concentration (ppm) | 1000 |
| O2 concentration (%) | 3 |
| Test temperature section (DEG C) | 150-450 |
Claims (9)
1. the method that one-step method prepares Cu based molecular sieve SCR catalysts, it is characterised in that：Using the SAPO-34 containing template
Molecular sieve slurry, by copper by the method for ion exchange in solution with Cu2+Form uniform load on molecular sieve, and the quality of copper
Fraction reaches 0.4-10.0%, by being once calcined, obtains Cu based molecular sieve SCR catalysts.
2. the method that one-step method prepares Cu based molecular sieve SCR catalysts, it is comprised the following steps that：
A) deionized water is added into synthesis SAPO-34 molecular sieve kettle liquids, quality solid content ultrasonic disperse, is obtained in 2-15%
Suspension；
B) suspension obtained by step a) is centrifuged, obtains solid；
C) deionized water is added to the solid obtained by step b), obtains the suspension that solid content is 5-15wt%；
D) compound nantokite is weighed, step c) gained suspensions is added, control the content of copper 0.1-1mol/L, stirs, obtain outstanding
Turbid；
E) alkali is added into suspension obtained by step d), adjusts pH to 4-6 while stirring；
F) by suspension high-speed stirred obtained by step e) and heat, carry out ion exchange in solution；
G) suspension obtained by step f) is centrifuged；
H) solid obtained by step g) is subjected to dewatered drying, ground, roasting, that is, obtain Cu based molecular sieve SCR catalysts.
3. according to the method for claim 2, it is characterised in that the ultrasonic power described in step (a) is 30-80kHz, is surpassed
The sound time is 0.5-3h.
4. according to the method for claim 2, it is characterised in that step (b) is 8000- with the centrifugation rate described in (g)
12000r/min, centrifugation time are 3-30min.
5. according to the method for claim 2, it is characterised in that alkali described in step (e) is ammoniacal liquor or tetramethyl hydroxide
Ammonium.
6. according to the method for claim 2, it is characterised in that the stir speed (S.S.) described in step (f) is 150-350r/
min；50-90 DEG C of heating-up temperature, hour duration 1.5-6.
7. according to the method for claim 2, it is characterised in that the drying temperature described in step (h) is 100-130 DEG C, is dried
Dry 1-5 hours；Sintering temperature is 400-800 DEG C, roasting time 2-6 hours.
8. according to the method for claim 2, it is characterised in that described synthesis SAPO-34 molecular sieves kettle liquid is that hydro-thermal is anti-
The kettle liquid of SAPO-34 molecular sieves should be prepared, solid phase reaction prepares the kettle liquid of SAPO-34 molecular sieves, gas phase reaction prepares SAPO-34
The kettle liquid of kettle liquid or SAPO-34 the molecular screen membranes production of molecular sieve.
9. according to the method described in claim 2, it is characterised in that described compound nantokite is sulfate, the nitre of copper of copper
Hydrochlorate, the villaumite of copper, the oxide of the acetate of copper or copper.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227540A (en) * | 2019-05-10 | 2019-09-13 | 四川大学 | AFI-CHA co-crystalline zeolite and using it as the NH of carrier3SCR catalyst and their preparation method |
| CN110479356A (en) * | 2019-07-17 | 2019-11-22 | 凯龙蓝烽新材料科技有限公司 | The Cu- molecular sieve SCR monolithic catalyst and preparation method thereof that a kind of nanometer of Cu impregnates in situ |
| CN111617801A (en) * | 2020-07-08 | 2020-09-04 | 黑龙江大学 | Preparation method of hierarchical porous Cu/SAPO-34 catalyst |
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2017
- 2017-11-06 CN CN201711075729.5A patent/CN107744830B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| TATSUMI ISHIHARA等: "Copper Ion-Exchanged SAPO-34 as a Thermostable Catalyst for Selective Reduction of NO with C3H6", 《JOURNAL OF CATALYSIS》 * |
| ZHI-MIN XING等: "Fabrication of Gold Nanoparticles in Confined Spaces using Solid-Phase Reduction: Significant Enhancement of Dispersion Degree and Catalytic Activity", 《CHEMICAL ENGINEERING SCIENCE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227540A (en) * | 2019-05-10 | 2019-09-13 | 四川大学 | AFI-CHA co-crystalline zeolite and using it as the NH of carrier3SCR catalyst and their preparation method |
| WO2020228652A1 (en) * | 2019-05-10 | 2020-11-19 | 四川大学 | Afi-cha mixed crystal molecular sieve and nh 3-scr catalyst using same as carrier, and preparation methods therefor |
| US11241675B2 (en) | 2019-05-10 | 2022-02-08 | Sichuan University | AFI-CHA hybrid crystal zeolite and NH3-SCR catalyst using same as carrier, and preparation methods thereof |
| CN110479356A (en) * | 2019-07-17 | 2019-11-22 | 凯龙蓝烽新材料科技有限公司 | The Cu- molecular sieve SCR monolithic catalyst and preparation method thereof that a kind of nanometer of Cu impregnates in situ |
| CN111617801A (en) * | 2020-07-08 | 2020-09-04 | 黑龙江大学 | Preparation method of hierarchical porous Cu/SAPO-34 catalyst |
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