CN110104658A - A kind of method directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing - Google Patents
A kind of method directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing Download PDFInfo
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- CN110104658A CN110104658A CN201910426727.9A CN201910426727A CN110104658A CN 110104658 A CN110104658 A CN 110104658A CN 201910426727 A CN201910426727 A CN 201910426727A CN 110104658 A CN110104658 A CN 110104658A
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- molecular sieve
- ssz
- catalyst
- alkali metal
- metal containing
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- 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 104
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 103
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 41
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000002194 synthesizing effect Effects 0.000 title claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 9
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 239000002585 base Substances 0.000 claims abstract description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 20
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 239000007767 bonding agent Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 6
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- GNUJKXOGRSTACR-UHFFFAOYSA-M 1-adamantyl(trimethyl)azanium;hydroxide Chemical group [OH-].C1C(C2)CC3CC2CC1([N+](C)(C)C)C3 GNUJKXOGRSTACR-UHFFFAOYSA-M 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 230000032683 aging Effects 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal cation Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 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
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J29/04—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
-
- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to material chemistry technical fields, and in particular to a method of directly synthesize the Cu-SSZ-13 molecular sieve and its catalyst of not alkali metal containing.Direct synthesis method of the invention first mixes copper source, deionized water and organic amine, stirring forms uniform aqueous solution, quaternary ammonium base, template, aluminium hydroxide and silicon source are then added thereto, it is stirred to form uniform mixed liquor, mixed liquor carries out crystallization under the hydrothermal condition of self-generated pressure and certain crystallization temperature, the Cu-SSZ-13 molecular sieve of not alkali metal containing is obtained, which can be applied directly to the catalyst on honeycomb substrate as SCR reaction without post-processing.The preparation process flow of the present invention not Cu-SSZ-13 molecular sieve of alkali metal containing is simple, the period is short, low energy consumption, the Cu-SSZ-13 molecular sieve of preparation has many advantages, such as that copper content is controllable, silica alumina ratio is adjustable, good hydrothermal stability, catalytic activity are high, has significant advantage in terms of the denitration of SCR reaction.
Description
Technical field
The invention belongs to material chemistry technical fields, and in particular to a kind of Cu-SSZ-13 for directly synthesizing not alkali metal containing
The method of molecular sieve and its catalyst.
Background technique
Nitrogen oxides (NOx) it is one of main atmosphere pollution, acid rain can be caused, formed in conjunction with hydrocarbons photochemical
Learn smog.NO in exhaust gas from diesel vehiclex70% or more of vehicle mass exhaust total quantity is accounted for, at present NOxMainly pass through ammonia selective catalysis
Reduction technique (NH3- SCR) removing.NH3The key core of SCR technology is catalyst, and Cu-SSZ-13 molecular sieve has micropore ruler
Very little and one-dimensional channel design shows excellent anti-HC poisoning and SCR catalytic activity, therefore becomes research hotspot in recent years.
The method of Cu-SSZ-13 mainly has conventional synthetic methods and one-step synthesis at present, both synthetic methods require in the feed
It introduces alkali metal cation and carrys out balance molecule sieve skeleton frame charge, then remove the gold of the alkali in molecular sieve by post-processing ion exchange
Belong to ion.Xie Lijuan et al.[1]It points out in high temperature thermal and hydric environment, the common anode ionization of alkali metal will lead in molecular sieve
Framework of molecular sieve dealuminzation and Cu2+Reunite and inactivates.
Be conventionally synthesized technique: 3 ~ 5 days hydrothermal synthesis SSZ-13 molecular sieves first are removed by centrifugation, drying, high-temperature roasting
Template, obtain M-SSZ-13(M indicate alkali metal), then M-SSZ-13 molecular sieve through ammonium ion-exchanged, centrifugation, do
Dry, high-temperature roasting obtains NH4- SSZ-13 molecular sieve, last NH4- SSZ-13 molecular sieve heats in copper salt solution carries out ion
Exchange, obtains Cu-SSZ-13 catalyst by centrifugation, drying, high-temperature roasting.The Cu-SSZ-13 catalysis of conventional synthetic methods preparation
The fresh state of agent and the SCR denitration of hydrothermal aging state are had excellent performance, however preparation process flow is complicated, energy consumption is high, the period is long, produces
Product yield is low, and the template used is expensive, and then leads to material high production cost.In addition, what is generated in last handling process is useless
Liquid will lead to water pollution, increase the cost of sewage treatment.
One-step synthesis technique: being that copper source is directly added into raw material first, synthesize M/Cu-SSZ-13 molecular sieve, by from
The heart, drying, roasting removed template method；Then ion exchange is carried out using nitric acid or ammonium salt, removes the part alkali gold in molecular sieve
Belong to ion, obtains final product Cu-SSZ-13 molecular sieve using centrifugation, drying, high-temperature roasting.In-situ synthesis is closed than tradition
Process flow is shortened at method, the production cost of Cu-SSZ-13 catalyst is considerably reduced using cheap template.However
The M/Cu-SSZ-13 molecular sieve silica alumina ratio of synthesis is low, alkali metal content is high, and aftertreatment technology can not be while controlling Cu content
Effectively removing alkali metal, and pickling can destroy framework of molecular sieve, generate silanol, significantly reduce catalytic activity.
One-step synthesis has extensive prospect because its production cost is low in terms of industrial application, therefore becomes in recent years
One of research hotspot.Wherein patent CN201510583531.2 and CN201380061272.6 describes one-step method preparation Cu-
CHA molecular sieve, however Na is introduced during the preparation process+Equal alkali metal cations.Patent CN201410058705.9 description
It is one-step method preparation Cu-CHA molecular sieve, describes have " phosphoric acid is added by the complete peptization of aluminium hydroxide ", " P in summary of the invention2O5,
0.8 ~ 1.1 mole ", the contents such as " product washs for several times, until cleaning solution is in neutrality ", illustrate that the patent of invention is mainly one-step method
Cu-SAPO-34 molecular sieve is synthesized, and crystallization product can not be directly used as catalyst material.Patent CN201610552897.8 is retouched
What is stated is one-step method preparation Cu-SSZ-13 molecular sieve, describes to have in summary of the invention and " repeatedly wash the progress of crystallization products therefrom straight
It is in neutrality to solution " or the contents such as " control product alkaline metal ion concentration ", illustrate the Cu-SSZ-13 molecule of the one-step synthesis method
Sieve can not be directly used as catalyst material.
Non-patent literature: [1]Applied Catalysis B: Environmental, 179(2015), 206-212.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of directly synthesis
The not method of the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing.Preparation process of the invention is simple, the period is short, energy consumption
Low, the Cu-SSZ-13 molecular sieve of the not alkali metal containing of preparation is with copper content is controllable, silica alumina ratio is adjustable, hydrothermal stability
Well, the advantages that catalytic activity is high does not need the catalyst coat that post-processing can be directly used as SCR reaction.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of Cu- directly synthesizing not alkali metal containing
The method of SSZ-13 molecular sieve and its catalyst, which is characterized in that the direct synthesis method has the feature that
A kind of method directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing, comprising the following steps:
(1) preparation of Cu-SSZ-13 molecular sieve:
A, copper source, deionized water and organic amine are mixed, stirring forms uniform aqueous solution, then to quaternary ammonium is added in mixed liquor
Alkali, template, aluminium hydroxide and silicon source simultaneously stir, and obtained uniform mixed liquor is in self-generated pressure, 140 ~ 200 DEG C of hydrothermal condition
Lower crystallization 24 ~ 120 hours, obtains molecular sieve mixed liquor；
B, obtained molecular sieve mixed liquor is separated, and 1 ~ 10 hour dry at 50 ~ 200 DEG C, then at 500 ~ 700 DEG C
Muffle kiln roasting 1 ~ 10 hour, obtained molecular sieve powder；
(2) the use of Cu-SSZ-13 system with molecular sieve for preparing includes two kinds for the method for catalyst:
Molecular sieve mixed liquor in step (a) is coated in honeycomb substrate with deionized water and bonding agent by (2-1) after mixing
On obtain molecular sieve catalyst；
The molecular sieve powder and deionized water and bonding agent that step (b) obtains are coated in honeycomb substrate by (2-2) after mixing
On obtain molecular sieve catalyst.
Copper source is one or more of copper sulphate, copper nitrate or copper acetate.
The organic amine is tetraethylenepentamine or other can form one or more of the primary amine of complex compound with copper.
The quaternary ammonium base is one of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide or tetrapropylammonium hydroxide or several
Kind.
The template is N, N, N- trimethyl-adamantyl ammonium hydroxide or benzyltrimethylammonium hydroxide.
The silicon source is one or more of silica, silica solution, ethyl orthosilicate or Y type molecular sieve.
Al in the aluminium hydroxide2O3With the mass ratio of the material of other raw materials are as follows: n(Cu2+)/n(Al2O3)=0.1 ~ 5, n
(organic amine)/n(Al2O3OH in)=0.1 ~ 5, n(quaternary ammonium base-)/n(Al2O3)=1 ~ 10, n(template)/n(Al2O3)=1 ~ 6, n
(SiO2)/n(Al2O3)=1 ~ 80, n(H2O)/n (Al2O3)=100~1000。
The separate mode of the molecular sieve mixed liquor is physics sedimentation, filters pressing or centrifugation.
The bonding agent is silica gel and aluminium glue, wherein presses mass parts ratio, molecular sieve: aluminium glue: silica gel=36% ~ 55%:5% ~
8%:25% ~ 35%.
Application of the standby catalyst of the Cu-SSZ-13 system with molecular sieve for preparing of the not alkali metal containing in SCR reaction.
Compared with prior art, the invention has the following advantages:
The present invention adjusts synthetic system pH by quaternary ammonium base, while in the synthesis process, the N (R) that quaternary ammonium caustic digestion generates3H+
Into in molecular sieve, balance skeleton charge increases the Bronsted acidic site of molecular sieve, enhances ammonia adsorption capacity, improves and divides
Son sieves catalytic activity at low temperature, does not contain alkali metal in raw material of the present invention, therefore do not need washing, alkali
The post-processings such as metal removal can be directly used as catalyst material.Preparation process of the invention is simple, the period is short, low energy consumption, system
The Cu-SSZ-13 molecular sieve of standby not alkali metal containing is with copper content is controllable, silica alumina ratio is adjustable, good hydrothermal stability, urges
Change the advantages that activity is high.
Detailed description of the invention
Fig. 1 is the XRD spectrum of the Cu-SSZ-13 molecular sieve of not alkali metal containing prepared by the embodiment of the present invention 1 ~ 4.
Fig. 2 is the XRD spectrum of the embodiment of the present invention 1 and the fresh state of comparative example 1 and aging state molecular sieve.
Fig. 3 is the catalytic performance of the embodiment of the present invention 1 and the fresh state of comparative example 1 and aging state molecular sieve.
Description of symbols: " " is the characteristic peak of SSZ-13 molecular sieve；"Cu-SSZ-13-1","Cu-SSZ-13-2",
" Cu-SSZ-13-3 " and " Cu-SSZ-13-4 " is the Cu-SSZ-13 molecular sieve of the not alkali metal containing of embodiment 1-4 preparation；"Cu-
SSZ-13-1 " and " Reference " are fresh state；" Cu-SSZ-13-1-A " and " Reference-A " is aging state.
Specific embodiment
Further description of the technical solution of the present invention with attached drawing combined with specific embodiments below.
Embodiment 1
A kind of method directly synthesizing the not Cu-SSZ-13 molecular sieve of alkali metal containing, comprising the following steps:
(1) copper sulphate and tetraethylenepentamine, deionized water are mixed first, is stirred to form uniform aqueous solution；
(2) tetramethylammonium hydroxide (TMAH), N, N, N- trimethyl-adamantyl hydrogen are added into the aqueous solution of step (1)
Amine-oxides, aluminium hydroxide and silica are stirred to form uniform mixed liquor, and wherein the mol ratio of raw material is n (Cu-
TEPA): n (SiO2): n (Al2O3): n (TMAH): n (H2O): n (C13H25NO)=0.1:80:1:1:1000:2；
(3) by the mixed liquor in step (2) crystallization 120 hours under self-generated pressure and 140 DEG C of hydrothermal condition, product is through object
Separated after reason sedimentation, obtaining wt (M) < 5ppm(M indicates alkali metal), wt (Cu)=4%, n (SiO2)/n(Al2O3The Cu- of)=20
SSZ-13 molecular sieve；
(4) molecular sieve in step (3) after dry 12h, is put into Muffle furnace, roasts 4 hours, obtains at 600 DEG C at 80 DEG C
To molecular sieve powder.
Embodiment 2
A kind of method directly synthesizing the not Cu-SSZ-13 molecular sieve catalyst of alkali metal containing, comprising the following steps:
(1) copper sulphate and tetraethylenepentamine, deionized water are mixed first, is stirred to form uniform aqueous solution；
(2) tetraethyl ammonium hydroxide, benzyltrimethylammonium hydroxide, aluminium hydroxide and silicon are added into the aqueous solution of step (1)
Colloidal sol is stirred to form uniform mixed liquor, and wherein the molar ratio of raw material is n (Cu-TEPA): n (SiO2):n(Al2O3):n
(TEAH):n(H2O):n(C10H17NO)=1:60:2:10:500:6；
(3) by the mixed liquor in step (2) crystallization 96 hours under self-generated pressure and 160 DEG C of hydrothermal condition, product is through pressing
Filter, 200 DEG C dry 3 hours, 500 DEG C roasting 10 hours after obtain wt (M) < 5 ppm(M indicate alkali metal), wt (Cu)=5%, n
(SiO2)/n(Al2O3The Cu-SSZ-13 molecular sieve of)=15；
(4) by step (3) molecular sieve addition deionized water, stir evenly after silica gel and aluminium glue, in slurries mass fraction it
Than for molecular sieve: aluminium glue: silica gel=36%:8%:35%, slurries are coated on honeycomb substrate and obtain molecular sieve catalyst.
Embodiment 3
A kind of method directly synthesizing the not Cu-SSZ-13 molecular sieve catalyst of alkali metal containing, comprising the following steps:
(1) copper nitrate and tetraethylenepentamine, deionized water are mixed first, is stirred to form uniform aqueous solution；
(2) the addition tetrapropylammonium hydroxide, N into the aqueous solution of step (1), N, N- trimethyl-adamantyl ammonium hydroxide,
Aluminium hydroxide and waterglass are stirred to form uniform mixed liquor, and wherein the molar ratio of raw material is n (Cu-TEPA): n
(SiO2):n(Al2O3):n(TPAOH):n(H2O):n(C13H25NO)=5:1:1:5:100:1；
(3) by the mixed liquor in step (2) crystallization 60 hours under self-generated pressure and 180 DEG C of hydrothermal condition, product pass through from
The heart, 80 DEG C dry 10 hours, 700 DEG C roasting 2 hours after obtain wt (M) < 5 ppm(M indicate alkali metal), wt (Cu)=10%, n
(SiO2)/n(Al2O3The Cu-SSZ-13 molecular sieve powder of)=3；
(4) by step (3) molecular sieve addition deionized water, stir evenly after silica gel and aluminium glue, in slurries mass fraction it
Than for molecular sieve: aluminium glue: silica gel=55%:5%:25%, slurries are coated on honeycomb substrate and obtain molecular sieve catalyst.
Embodiment 4
A kind of method directly synthesizing the not Cu-SSZ-13 molecular sieve catalyst of alkali metal containing, comprising the following steps:
(1) copper acetate and tetraethylenepentamine, deionized water are mixed first, is stirred to form uniform aqueous solution；
(2) tetramethylammonium hydroxide, benzyltrimethylammonium hydroxide, aluminium hydroxide and just are added into the aqueous solution of step (1)
Silester is stirred to form uniform mixed liquor, and wherein the molar ratio of raw material is n (Cu-TEPA): n (SiO2):n
(Al2O3):n(TMAH):n(H2O):n(C10H17NO)=2:40:1:8:300:4；
(3) mixed liquor in step (2) is obtained for crystallization 24 hours under self-generated pressure and 200 DEG C of hydrothermal condition without alkali
The mixed liquor of the Cu-SSZ-13 molecular sieve of metal；
(4) it will be stirred evenly after molecular sieve mixed liquor addition deionized water, silica gel and the aluminium glue in step (3), quality in slurries
The ratio between number is molecular sieve: aluminium glue: silica gel=36%:5%:25%, and slurries are coated on honeycomb substrate and obtain molecular sieve catalyst.
Comparative example 1
Molecular sieve in this example is prepared using the preparation method of bibliography, and the molar ratio of Primogel is Na2O :
Al2O3 : H2O : SiO2 : Cu-TEPA=14.8:3.0:600:30:4, molecular sieve obtained are denoted as Reference molecular sieve.
Bibliography:Chinese Journal of Catalysis, 2012,33(1): 92-105.
Reference prepared by the Cu-SSZ-13 molecular sieve of not alkali metal containing prepared by embodiment 1 and comparative example 1 points
Son sieve carries out hydrothermal aging, and the catalytic performance carried out under fresh state and ageing state is compared, wherein hydrothermal aging item
Part: the Reference molecular sieve prepared in fresh state Cu-SSZ-13-1 molecular sieve and comparative example 1 prepared by the embodiment of the present invention 1
It is placed in tube furnace, through 750 DEG C, 10%H216 h of air atmosphere aging of O obtain aging state " Cu-SSZ-13-1-A " and
"Reference-A".Wherein, catalytic performance test condition: atmosphere is 450 ppm NO, 450 ppm NH3、14% O2、5%
CO2、3% H2O, remaining N2、GHSV=168000 h-1；Evaluation temperature range is 130 DEG C ~ 600 DEG C, 10 DEG C/min of heating rate.
Fig. 1 is the XRD spectrum of the Cu-SSZ-13 molecular sieve of not alkali metal containing prepared by the embodiment of the present invention 1 ~ 4.From Fig. 1
XRD spectrum can be seen that 1-4 of the embodiment of the present invention successfully synthesizes the Cu-SSZ-13 molecular sieve of not alkali metal containing.
Fig. 2 is the XRD spectrum of the embodiment of the present invention 1 and the fresh state of comparative example 1 and aging state molecular sieve.It can from Fig. 2
There can be no characteristic peaks for the XRD spectrum of " Reference-A " molecular sieve after aging out, after this illustrates aging
" Reference-A " molecular sieve structure has been destroyed, and the characteristic peak of " Cu-SSZ-13-1-A " XRD spectrum after aging with
The characteristic peak of fresh state fits like a glove, the stable structure of this explanation " Cu-SSZ-13-1 " molecular sieve prepared by the present invention.
Fig. 3 is the catalytic performance of the embodiment of the present invention 1 and the fresh state of comparative example 1 and aging state molecular sieve.It can from Fig. 3
Out, when temperature is lower than 300 DEG C, the catalytic performance of fresh state " Cu-SSZ-13-1 " is better than fresh state " Reference " molecule
Sieve；When temperature is between 300 DEG C and 525 DEG C, the catalytic performance of fresh state " Cu-SSZ-13-1 " and " Reference " are differed
Very few, when temperature is higher than 525 DEG C, " catalytic performance of Cu-SSZ-13-1 is better than fresh state " Reference " molecule to fresh state
Sieve；But the catalytic performance of " Reference " molecular sieve Jing Guo aging is almost 0, well below " Cu-SSZ- after aging
The catalytic performance of 13-1 ".
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this
Under the inventive concept of invention, using equivalent structure transformation made by present specification, or directly/it is used in other indirectly
Relevant technical field is included in scope of patent protection of the invention.
Claims (10)
1. a kind of method for directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing, which is characterized in that including
Following steps:
(1) preparation of Cu-SSZ-13 molecular sieve:
A, copper source, deionized water and organic amine are mixed, stirring forms uniform aqueous solution, then to quaternary ammonium is added in mixed liquor
Alkali, template, aluminium hydroxide and silicon source simultaneously stir, and obtained uniform mixed liquor is in self-generated pressure, 140 ~ 200 DEG C of hydrothermal condition
Lower crystallization 24 ~ 120 hours, obtains molecular sieve mixed liquor；
B, obtained molecular sieve mixed liquor is separated, and 1 ~ 10 hour dry at 50 ~ 200 DEG C, then at 500 ~ 700 DEG C
Muffle kiln roasting 1 ~ 10 hour, obtained molecular sieve powder；
(2) the use of Cu-SSZ-13 system with molecular sieve for preparing includes two kinds for the method for catalyst:
Molecular sieve mixed liquor in step (a) is coated in honeycomb substrate with deionized water and bonding agent by (2-1) after mixing
On obtain molecular sieve catalyst；
The molecular sieve powder and deionized water and bonding agent that step (b) obtains are coated in honeycomb substrate by (2-2) after mixing
On obtain molecular sieve catalyst.
2. the method according to claim 1 for directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing,
It is characterized in that, copper source is one or more of copper sulphate, copper nitrate or copper acetate.
3. the method according to claim 1 for directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing,
It is characterized in that, the organic amine is tetraethylenepentamine or other can form one or more of the primary amine of complex compound with copper.
4. the method according to claim 1 for directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing,
It is characterized in that, the quaternary ammonium base is one of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide or tetrapropylammonium hydroxide
Or it is several.
5. the method according to claim 1 for directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing,
It is characterized in that, the template is N, N, N- trimethyl-adamantyl ammonium hydroxide or benzyltrimethylammonium hydroxide.
6. the method according to claim 1 for directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing,
It is characterized in that, the silicon source is one or more of silica, silica solution, ethyl orthosilicate or Y type molecular sieve.
7. the method according to claim 1 for directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing,
It is characterized in that, the Al in the aluminium hydroxide2O3With the mass ratio of the material of other raw materials are as follows: n(Cu2+)/n(Al2O3)=0.1 ~
5, n(organic amines)/n(Al2O3OH in)=0.1 ~ 5, n(quaternary ammonium base-)/n(Al2O3)=1 ~ 10, n(template)/n(Al2O3)=1 ~
6, n(SiO2)/n(Al2O3)=1 ~ 80, n(H2O)/n (Al2O3)=100~1000。
8. the method according to claim 1 for directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing,
It is characterized in that, the separate mode of the molecular sieve mixed liquor is physics sedimentation, filters pressing or centrifugation.
9. the method according to claim 1 for directly synthesizing not the Cu-SSZ-13 molecular sieve and its catalyst of alkali metal containing,
It is characterized in that, the bonding agent is silica gel and aluminium glue, wherein press mass parts ratio, molecular sieve: aluminium glue: silica gel=36% ~ 55%:
5% ~ 8%:25% ~ 35%.
10. the standby catalyst of the Cu-SSZ-13 system with molecular sieve for preparing of the described in any item not alkali metal containings of claim 1 ~ 9 is anti-in SCR
Application in answering.
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