CN106215974A - A kind of preparation method of copper Fe compound type SAPO 34 molecular sieve catalyst - Google Patents
A kind of preparation method of copper Fe compound type SAPO 34 molecular sieve catalyst Download PDFInfo
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- CN106215974A CN106215974A CN201610539337.9A CN201610539337A CN106215974A CN 106215974 A CN106215974 A CN 106215974A CN 201610539337 A CN201610539337 A CN 201610539337A CN 106215974 A CN106215974 A CN 106215974A
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- molecular sieve
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- cusapo
- deionized water
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- 239000010949 copper Substances 0.000 title claims abstract description 54
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 52
- 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 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 241000269350 Anura Species 0.000 title abstract 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 39
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 32
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000002505 iron Chemical class 0.000 claims abstract description 31
- 239000012265 solid product Substances 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- 238000001935 peptisation Methods 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- 230000001105 regulatory effect Effects 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims description 38
- -1 iron ion Chemical class 0.000 claims description 28
- 229910052742 iron Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 13
- 238000001308 synthesis method Methods 0.000 claims description 13
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910001868 water Inorganic materials 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000011833 salt mixture Substances 0.000 abstract 1
- 229920001940 conductive polymer Polymers 0.000 description 18
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 16
- 229910002651 NO3 Inorganic materials 0.000 description 12
- 238000010792 warming Methods 0.000 description 9
- 229910002012 Aerosil® Inorganic materials 0.000 description 8
- 229920000265 Polyparaphenylene Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910016374 CuSO45H2O Inorganic materials 0.000 description 2
- 229910017827 Cu—Fe Inorganic materials 0.000 description 2
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052676 chabazite Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the preparation method of a kind of copper Fe compound type SAPO 34 molecular sieve catalyst, comprise the following steps: boehmite is sufficiently stirred in deionized water, add phosphoric acid by its complete peptization, add silicon dioxide and mantoquita stirs, add triethylamine and TEPA and stir, loading crystallization in reactor after stirring, gained is CuSAPO 34 molecular sieve；Add iron salt or ferrum copper salt-mixture in deionized water, by dropping ammonia, the pH value of saline solution is regulated to 1 ~ 6；Saline solution is mixed with CuSAPO 34 molecular sieve, water bath with thermostatic control subsequently, by scrubbed for the solid product of gained, dry and roasting, obtain copper Fe compound type SAPO 34 molecular sieve catalyst.The present invention the most significantly simplifies technical process, has saved cost, it is achieved that widen NOxConversion temperature window object, improves the sulfur tolerance of catalyst.
Description
Technical field
The invention belongs to method for preparing catalyst technical field, present invention relates especially to a kind of exhaust gas from diesel vehicle NOx and urge
Change the preparation method of reduction Cu-Fe compound SAPO-34 molecular sieve catalyst.
Background technology
The NO of discharge in vehicle exhaustxHuman and environment is had the biggest harm, along with development and people's environmental protection meaning of society
Knowing constantly to strengthen, automotive emission is required to heal to become strict by the laws and regulations of various countries.In order to meet laws and regulations requirement, reduce
The NO of motor vehicle exhaust emissionxAmount, NH3-SCR, as maximally efficient method, is widely used in NOxCatalysis reduction.Along with tail gas
The continuous upgrading of discharge standard, molecular sieve carried transition metal has obtained the height of Chinese scholars as SCR catalyst material
Degree is paid attention to, especially chabazite molecular sieve, because of its high activity and stability, becomes selective reduction catalysis NOxThe future converted
One of developing direction.
The molecular sieve of carrying transition metal copper, shows superior low-temperature SCR catalysis activity, and iron-based molecular sieve shows
Good high temp effect and Sulfur tolerance.Therefore in actual SCR research, typically there is the chabasie catalyst of three types.A kind of
It is the catalyst of supported copper, NO under low temperaturexTransformation efficiency ratio is more prominent；The second is the catalyst of load iron, high temperature section NOxTurn
Change efficiency to have superiority, and have good Sulfur tolerance；The third combines two kinds of metals of copper ferrum exactly, has widened whole NOxConvert temperature
Degree window, and strengthen the Sulfur tolerance of catalyst.
Method disclosed in patent CN102614910A is first to synthesize SAPO-34 molecular sieve, then molecular sieve is exchanged into NH4
Type, more repeatedly exchange with copper, iron salt solutions, it is thus achieved that the SAPO-34 molecular sieve of supported copper ferrum.Patent CN103008002A is public
Open with ZSM-5, SSZ-13, SAPO-34, MOR or Beta molecular sieve as catalyst carrier, used ion exchange to prepare respectively
Copper-based catalysts and ferrum-based catalyst, then, use the standby Fe molecular sieve catalyst of mechanical type series system and Cu molecular sieve catalytic
Agent.
Number of patent application CN104971766A discloses by one-step method directly during synthesis chabazite molecular sieve
It is incorporated to ferrum, then is incorporated to copper by the mode of ion exchange.Although said method can obtain copper Fe compound type molecule to a certain extent
Sieve, embodies copper iron molecule and sieves at NOxAdvantage in conversion.But there is also following problem: first can not be evenly distributed, Cu
The molecular sieve that content is controlled, due to content and the distribution most important property to SCR low-temperature zone in actual applications of copper, the most right
The impact of performance is the most clearly；Secondly Fe load capacity over a molecular sieve and position are wayward；Last Cu-Fe compound molecule
The preparation method process of sieve catalyst is complicated, it is more difficult to industrialization, the structural stability of molecular sieve is affected.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that one can significantly process simplification,
The preparation method of cost-effective copper Fe compound type SAPO-34 molecular sieve catalyst.
The technical scheme provided according to the present invention, the preparation method of described copper Fe compound type SAPO-34 molecular sieve catalyst
Comprise the following steps:
A1, boehmite is sufficiently stirred in deionized water, is subsequently adding phosphoric acid by complete for boehmite peptization, treats glue
It is dissolved complete rear addition silicon dioxide and mantoquita stirs, be subsequently adding triethylamine and TEPA and stir, filling after stirring
Entering crystallization in reactor, gained is CuSAPO-34 molecular sieve；
B1, it is the mixture that 1:1 adds iron salt and mantoquita in deionized water by the mol ratio of iron salt and mantoquita, obtains copper iron salt
Solution so that in copper iron salt solutions, the mass fraction of iron ion is 0.5% ~ 3%, is the ammonia of 15% ~ 25% by dropping mass fraction
The pH value of copper iron salt solutions is regulated to 1 ~ 6 by water；
C1, by [Fe3+] with the mole ratio of [CuSAPO-34] be 0.5 ~ 3:1 by copper iron salt solutions with one-step synthesis method
Stirring 1 ~ 3h after the mixing of CuSAPO-34 molecular sieve, 60 ~ 85 DEG C of water-bath 0.5 ~ 4h of constant temperature, obtain solid product subsequently；
D1, by the solid product of gained through deionized water wash, until cleaning mixture is to neutral；
E1, solid product is put in 80 ~ 150 DEG C of baking ovens be dried 5 ~ 12 hours, subsequently with the programming rate liter of 3 ~ 10 DEG C/min
Temperature was to 400 ~ 650 DEG C of roastings 2 ~ 10 hours, and roasting terminates, and obtains copper Fe compound type SAPO-34 molecular sieve catalyst.
Described iron salt is the one or two kinds of in solubility ferric nitrate, iron chloride；And copper nitrate that mantoquita is solubility,
One or both in Schweinfurt green, copper sulfate, copper chloride, copper acetate.
The preparation method of a kind of copper Fe compound type SAPO-34 molecular sieve catalyst can comprise the further steps of:
A2, boehmite is sufficiently stirred in deionized water, is subsequently adding phosphoric acid by complete for boehmite peptization, treats glue
It is dissolved complete rear addition silicon dioxide and mantoquita stirs, be subsequently adding triethylamine and TEPA and stir, filling after stirring
Entering crystallization in reactor, gained is CuSAPO-34 molecular sieve；
B2, add iron salt in deionized water, obtain iron salt solutions so that in iron salt solutions, the mass fraction of iron ion is 0.5%
~ 3%, by the ammonia that dropping mass fraction is 15% ~ 25%, the pH value of solution is regulated to 1 ~ 6；
C2, by [Fe3+] it is 0.5 ~ 3:1 by iron salt solutions with the CuSAPO-of one-step synthesis method with the mol ratio of [CuSAPO-34]
Stirring 1 ~ 3h after 34 molecular sieve mixing, 60 ~ 85 DEG C of water-bath 0.5 ~ 4h of constant temperature, obtain solid product subsequently；
D2, by the solid product of gained through deionized water wash, until cleaning mixture is to neutral；
E2, solid product is put in 80 ~ 150 DEG C of baking ovens be dried 5 ~ 12 hours, subsequently with the programming rate liter of 3 ~ 10 DEG C/min
Temperature was to 400 ~ 650 DEG C of roastings 2 ~ 10 hours, and roasting terminates, and obtains copper Fe compound type SAPO-34 molecular sieve catalyst.
Described iron salt is the one or two kinds of in solubility ferric nitrate, iron chloride.
The present invention passes through one-step synthesis method CuSAPO-34, and it is compound only need to i.e. to achieve Cu/Fe through primary ions exchange
Type SAPO-34 molecular sieve catalyst, the most significantly simplifies technical process, has saved cost, it is achieved that widen NOxConversion temperature
Window object, improves the sulfur tolerance of catalyst.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention and comparative example prepare sample NOx catalytic result comparison diagram.Experiment uses fixed bed micro-
Deinstall, MKS2030 Fourier transform infrared analyser carry out fresh state and the aging NH of sulfur respectively to catalyst fines3-SCR
During NOx conversion situation experiment, experiment condition is respectively as follows: air speed 200000 h-1, NO 500ppm, NH3 500ppm 、14%
O2、5% H2O、5% CO2, N2As balanced gas；Air speed 200000 h-1, NO 500ppm, NH3 500ppm 、SO2 20ppm
、14% O2、5% H2O、5% CO2, N2As balanced gas.
Fig. 2 is that the catalyst prepared of the present invention is at the aging lower NO of sulfurxConversion rate curve figure.
Fig. 3 is the copper ferrum loadings figure of the ICP measurement of all embodiments of the invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
A1, boehmite is sufficiently stirred in deionized water, is subsequently adding phosphoric acid by complete for boehmite peptization, treats glue
It is dissolved complete rear addition aerosil and Schweinfurt green stirs, be subsequently adding triethylamine and TEPA and stir, intending
The mol ratio of boehmite, deionized water, phosphoric acid, silicon dioxide, Schweinfurt green, triethylamine and TEPA is 0.9:1.0:
0.5:3.0:0.3:0.1:80, is incorporated with in the stainless steel cauldron of tetrafluoroethene or polyparaphenylene liner after stirring 5 hours, will
This reactor is crystallization 3.5 days under conditions of 200 DEG C, and gained is CuSAPO-34 molecular sieve；The CuSAPO-34 of gained is divided
Son sieve utilizes ICP to detect the content of wherein metal, is 2.8% through measuring copper content；
B1, by Fe (NO3)39H2O and Cu (NO3)23H2O mixes with deionized water, Fe (NO3)39H2O and Cu (NO3)23H2O
Mol ratio be 1:1 so that in copper iron salt solutions, the mass fraction of iron ion is 3%, by dropping mass fraction be the ammonia of 25%
Copper iron salt solutions is regulated pH to 6 by water；
C1, by [Fe3+] and [CuSAPO-34] mol ratio be that copper iron salt solutions is divided by 3:1 with the CuSAPO-34 of one-step synthesis method
Son sieve mixing, stirs 3h, and 85 DEG C of water-bath 4h of constant temperature, obtain solid product subsequently；
D1, the solid product of gained is washed through for several times, until cleaning mixture is to neutral；
E1, solid product is put in 150 DEG C of baking ovens be dried 12h, be warming up to 650 DEG C of roastings with the programming rate of 3 DEG C/min subsequently
Burning 2h, preparation completes.
Utilizing ICP to detect the content of wherein metal the catalyst of gained, be 2.21% through measuring copper content, iron content is
1.84%。
Embodiment 2
A1, boehmite is stirred in deionized water, be subsequently adding phosphoric acid by complete for boehmite peptization；Treat that peptization is complete
Add aerosil after complete and Schweinfurt green stirs, be subsequently adding triethylamine and TEPA and stir, intending thin water
The mol ratio of aluminum stone, deionized water, phosphoric acid, silicon dioxide, Schweinfurt green, triethylamine and TEPA is 0.9:1.0:0.5:
3.0:0.3:0.1:80, is incorporated with in the stainless steel cauldron of tetrafluoroethene or polyparaphenylene liner after stirring 5 hours, and this is anti-
Answering still crystallization 3.5 days under the conditions of 200 DEG C, gained is CuSAPO-34 molecular sieve；CuSAPO-34 molecular sieve profit to gained
Detect the content of wherein metal with ICP, be 2.8% through measuring copper content；
B1, by Fe (NO3)39H2O and Cu (Cl)22H2O mixes with deionized water, Fe (NO3)39H2O and Cu (Cl)22H2O's
Mol ratio is 1:1 so that in copper iron salt solutions, the mass fraction of iron ion is 2%, is the ammonia of 20% by dropping mass fraction
Copper iron salt solutions is regulated pH to 4；
C1, by [Fe3+] and [CuSAPO-34] mol ratio to be 3:1 mix saline solution with the Cu-SAPO34 of one-step synthesis method, stir
Mix 2.5h, subsequently 80 DEG C of water-bath 3h of constant temperature；
D1, the product of gained is washed through for several times, until last cleaning mixture is to neutral；
E1, solid product is put in 120 DEG C of baking ovens be dried 10h, be warming up to 600 DEG C of roastings with the programming rate of 5 DEG C/min subsequently
Burning 4h, preparation completes.
Utilizing ICP to detect the content of wherein metal the catalyst of gained, be 2.35% through measuring copper content, iron content is
1.37%。
Embodiment 3
A1, boehmite is sufficiently stirred in deionized water, is then slowly added into phosphoric acid by complete for boehmite peptization；
After peptization is complete, adds aerosil and Schweinfurt green stirs, be subsequently adding triethylamine and TEPA is the most violent
Stirring；The mol ratio of boehmite, deionized water, phosphoric acid, silicon dioxide, Schweinfurt green, triethylamine and TEPA is
0.9:1.0:0.5:3.0:0.3:0.1:80, the rustless steel being incorporated with tetrafluoroethene or polyparaphenylene liner after stirring 5 hours is anti-
Answer in still；By this reactor 200 DEG C of crystallization 3.5 days, gained is CuSAPO-34 molecular sieve；The CuSAPO-34 of gained is divided
Son sieve utilizes ICP to detect the content of wherein metal, is 2.8% through measuring copper content.
B1, by Fe (NO3)39H2O and Cu (CH3COO)2H2O mixes with deionized water, Fe (NO3)39H2O and Cu
(CH3COO)2H2The mol ratio of O is 1:1 so that in copper iron salt solutions, the mass fraction of iron ion is 1.5%, by dropping quality
Mark is that the ammonia of 18% is by copper iron salt solutions regulation pH to 2；
C1, by [Fe3+] and [CuSAPO-34] mol ratio be 1.5:1 by copper iron salt solutions with the CuSAPO-34 of one-step synthesis method
Mixing, stirs 1.5h, subsequently 70 DEG C of water-bath 2h of constant temperature；
D1, the product of gained is washed through for several times, until last cleaning mixture is to neutral；
E1, solid product is put in 100 DEG C of baking ovens be dried 8h, be warming up to 550 DEG C of roastings with the programming rate of 8 DEG C/min subsequently
8h, preparation completes；
Utilizing ICP to detect the content of wherein metal the catalyst of gained, be 2.5% through measuring copper content, iron content is 0.9%.
Embodiment 4
A1, boehmite is sufficiently stirred in deionized water, is then slowly added into phosphoric acid by complete for boehmite peptization；
After peptization is complete, adds aerosil and Schweinfurt green stirs, be subsequently adding triethylamine and TEPA is the most violent
Stirring；The mol ratio of boehmite, deionized water, phosphoric acid, silicon dioxide, Schweinfurt green, triethylamine and TEPA is
0.9:1.0:0.5:3.0:0.3:0.1:80, the rustless steel being incorporated with tetrafluoroethene or polyparaphenylene liner after stirring 5 hours is anti-
Answer in still；By this reactor 200 DEG C of crystallization 3.5 days, gained is CuSAPO-34 molecular sieve；The CuSAPO-34 of gained is divided
Son sieve utilizes ICP to detect the content of wherein metal, is 2.8% through measuring copper content；
B1, first by Fe (NO3)39H2O and CuSO45H2O mixes with deionized water, Fe (NO3)39H2O and CuSO45H2O rubs
Your ratio is 1:1 so that the saline solution of the mass fraction 0.5% of iron ion in copper iron salt solutions, is 15% by dropping mass fraction
Ammonia by copper iron salt solutions regulate pH to 1；
C1, by [Fe3+] and [CuSAPO-34] mol ratio be 0.5:1 by copper iron salt solutions with the CuSAPO-34 of one-step synthesis method
Mixing, stirs 1h, subsequently 60 DEG C of water-bath 0.5h of constant temperature；
D1, the product of gained is washed through for several times, until last cleaning mixture is to neutral；
E1, solid product is put in 80 DEG C of baking ovens be dried 5h, be warming up to 400 DEG C of roastings with the programming rate of 10 DEG C/min subsequently
10h, preparation completes.
Utilizing ICP to detect the content of wherein metal the catalyst of gained, be 2.65% through measuring copper content, iron content is
0.36%。
Embodiment 5
A2, boehmite is sufficiently stirred in deionized water, is then slowly added into phosphoric acid by complete for boehmite peptization；
After peptization is complete, adds aerosil and Schweinfurt green stirs, be subsequently adding triethylamine and TEPA is the most violent
Stirring；Boehmite, deionized water, phosphoric acid, silicon dioxide, Schweinfurt green, triethylamine and TEPA mol ratio
For 0.9:1.0:0.5:3.0:0.3:0.1:80, after stirring 5 hours, it is incorporated with tetrafluoroethene or the rustless steel of polyparaphenylene liner
In reactor；By this reactor 200 DEG C of crystallization 3.5 days, gained is CuSAPO-34 molecular sieve；Catalyst profit to gained
Detect the content of wherein metal with ICP, be 2.8% through measuring copper content；
B2, by Fe (cl)36H2O mixes with deionized water, obtains iron salt solutions so that in iron salt solutions, the quality of iron ion is divided
Number is 0.5%, is that iron salt solutions is regulated pH to 1 by the ammonia of 15% by dropping mass fraction；
C2, by [Fe3+] and [CuSAPO-34] mol ratio be that iron salt solutions is mixed by 0.5:1 with the CuSAPO-34 of one-step synthesis method
Close, stir 1h, subsequently 60 DEG C of water-bath 0.5h of constant temperature；
D2, the product of gained is washed through for several times, until last cleaning mixture is to neutral；
E2, solid product is put in 80 DEG C of baking ovens be dried 12h, be warming up to 400 DEG C of roastings with the programming rate of 10 DEG C/min subsequently
Burning 10h, preparation completes.
Utilizing ICP to detect the content of wherein metal the catalyst of gained, be 2.61% through measuring copper content, iron content is
0.73%。
Embodiment 6
A2, boehmite is sufficiently stirred in deionized water, is then slowly added into phosphoric acid by complete for boehmite peptization；
After peptization is complete, adds aerosil and Schweinfurt green stirs, be subsequently adding triethylamine and TEPA is the most violent
Stirring；The mol ratio of boehmite, deionized water, phosphoric acid, silicon dioxide, Schweinfurt green, triethylamine and TEPA is
0.9:1.0:0.5:3.0:0.3:0.1:80, the rustless steel being incorporated with tetrafluoroethene or polyparaphenylene liner after stirring 5 hours is anti-
Answer in still；By this reactor 200 DEG C of crystallization 3.5 days, gained is CuSAPO-34 molecular sieve；The CuSAPO-34 of gained is divided
Son sieve utilizes ICP to detect the content of wherein metal, is 2.8% through measuring copper content；
B2, by Fe (cl)36H2O mixes with deionized water, obtains iron salt solutions so that in iron salt solutions, the quality of iron ion is divided
Number is 1.5%, is that iron salt solutions is regulated pH to 2 by the ammonia of 18% by dropping mass fraction；
C2, by [Fe3+] and [CuSAPO-34] mol ratio to be 1:1 mix iron salt solutions with the CuSAPO-34 of one-step synthesis method,
Stirring 1.5h, subsequently 70 DEG C of water-bath 2h of constant temperature；
D2, the product of gained is washed through for several times, until last cleaning mixture is to neutral；
E2, solid product is put in 100 DEG C of baking ovens be dried 8h, be warming up to 550 DEG C of roastings with the programming rate of 8 DEG C/min subsequently
8h, preparation completes.
Utilizing ICP to detect the content of wherein metal the catalyst of gained, be 2.49% through measuring copper content, iron content is
1.04%。
Embodiment 7
A2, boehmite is sufficiently stirred in deionized water, is then slowly added into phosphoric acid by complete for boehmite peptization；
After peptization is complete, adds aerosil and Schweinfurt green stirs, be subsequently adding triethylamine and TEPA is the most violent
Stirring；The mol ratio of boehmite, deionized water, phosphoric acid, silicon dioxide, Schweinfurt green, triethylamine and TEPA is
0.9:1.0:0.5:3.0:0.3:0.1:80, the rustless steel being incorporated with tetrafluoroethene or polyparaphenylene liner after stirring 5 hours is anti-
Answer in still；By this reactor 200 DEG C of crystallization 3.5 days, gained is CuSAPO-34 molecular sieve；The catalyst of gained is utilized
In ICP detection CuSAPO-34 molecular sieve, the content of metal, is 2.8% through measuring copper content；
B2, by Fe (NO3)39H2O mixes with deionized water, obtains iron salt solutions so that in iron salt solutions, the quality of iron ion is divided
Number is 2%, is that iron salt solutions is regulated pH to 4 by the ammonia of 20% by dropping mass fraction；
C2, by [Fe3+] and [CuSAPO-34] mol ratio to be 2:1 mix saline solution with the CuSAPO-34 of one-step synthesis method, stir
Mix 2.5h, subsequently 80 DEG C of water-bath 3h of constant temperature；
D2, the product of gained is washed through for several times, until last cleaning mixture is to neutral；
E2, solid product is put in 120 DEG C of baking ovens be dried 10h, be warming up to 600 DEG C of roastings with the programming rate of 5 DEG C/min subsequently
Burning 4h, preparation completes.
Utilizing ICP to detect the content of wherein metal the catalyst of gained, be 2.27% through measuring copper content, iron content is
1.5%。
Embodiment 8
A2, boehmite is sufficiently stirred in deionized water, is then slowly added into phosphoric acid by complete for boehmite peptization；
After peptization is complete, adds aerosil and Schweinfurt green stirs, be subsequently adding triethylamine and TEPA is the most violent
Stirring；The mol ratio of boehmite, deionized water, phosphoric acid, silicon dioxide, Schweinfurt green, triethylamine and TEPA is
0.9:1.0:0.5:3.0:0.3:0.1:80, the rustless steel being incorporated with tetrafluoroethene or polyparaphenylene liner after stirring 5 hours is anti-
Answer in still；By this reactor 200 DEG C of crystallization 3.5 days, gained is CuSAPO-34 molecular sieve；The catalyst of gained is utilized
In ICP detection CuSAPO-34 molecular sieve, the content of metal, is 2.8% through measuring copper content；
B2, by Fe (NO3)39H2O mixes with deionized water, obtains iron salt solutions so that in iron salt solutions, the quality of iron ion is divided
Number is 3%, is that iron salt solutions is regulated pH to 6 by the ammonia of 25% by dropping mass fraction；
C2, by [Fe3+] and [CuSAPO-34] mol ratio to be 3:1 mix saline solution with the CuSAPO-34 of one-step synthesis method, stir
Mix 3h, subsequently 85 DEG C of water-bath 4h of constant temperature；
D2, the product of gained is washed through for several times, until last cleaning mixture is to neutral；
E2, solid product is put in 150 DEG C of baking ovens be dried 12h, be warming up to 650 DEG C of roastings with the programming rate of 3 DEG C/min subsequently
Burning 2h, preparation completes.
Utilizing ICP to detect the content of wherein metal the catalyst of gained, be 1.88% through measuring copper content, iron content is
2.01%。
Comparative example
Fe(NO3)39H2O and Cu (CH3COO)2H2O is according to mol ratio [Fe3+]/[Cu2+]=1 mixes with deionized water, prepares matter
Amount mark is the saline solution of 3%, by the ammonia regulation pH to 6 that dropping mass fraction is 25%.By mixing salt solution and certain business
Hydrogen SAPO-34 mixes, and stirs 3h, subsequently 85 DEG C of water-bath 4h of constant temperature；
The product of gained is washed through for several times, until last cleaning mixture is to neutral, solid product is put in 150 DEG C of baking ovens
Being dried 12h, be warming up to 650 DEG C of roasting 2h with the programming rate of 3 DEG C/min subsequently, preparation completes.
Utilizing ICP to detect the content of wherein metal the catalyst of gained, be 1.06% through measuring copper content, iron content is
1.55%。
It will be seen from figure 1 that the comparative example transformation efficiency relatively embodiment of the present invention 1 is compared and is significantly decreased, it is seen that multistep
Ion exchange is not effectively realized the uniform load of active component.
Figure it is seen that catalyst prepared by the present invention has under whole temperature window in the aging lower conversion rate of NOx of sulfur
There is greater advantage.
From figure 3, it can be seen that by the control to technological parameter, it is possible to achieve effectively control the load capacity of metal.
Claims (4)
1. a preparation method for copper Fe compound type SAPO-34 molecular sieve catalyst, is characterized in that this preparation method includes following
Step:
A1, boehmite is sufficiently stirred in deionized water, is subsequently adding phosphoric acid by complete for boehmite peptization, treats glue
It is dissolved complete rear addition silicon dioxide and mantoquita stirs, be subsequently adding triethylamine and TEPA and stir, filling after stirring
Entering crystallization in reactor, gained is CuSAPO-34 molecular sieve；
B1, it is the mixture that 1:1 adds iron salt and mantoquita in deionized water by the mol ratio of iron salt and mantoquita, obtains slaine
Solution so that in metallic solution, the mass fraction of iron ion is 0.5% ~ 3%, is the ammonia of 15% ~ 25% by dropping mass fraction
The pH value of solution is regulated to 1 ~ 6；
C1, by [Fe3+] with the mole ratio of [CuSAPO-34] be 0.5 ~ 3:1 by metal salt solution with one-step synthesis method
Stirring 1 ~ 3h after the mixing of CuSAPO-34 molecular sieve, 60 ~ 85 DEG C of water-bath 0.5 ~ 4h of constant temperature, obtain solid product subsequently；
D1, by the solid product of gained through deionized water wash, until cleaning mixture is to neutral；
E1, solid product is put in 80 ~ 150 DEG C of baking ovens be dried 5 ~ 12 hours, subsequently with the programming rate liter of 3 ~ 10 DEG C/min
Temperature was to 400 ~ 650 DEG C of roastings 2 ~ 10 hours, and roasting terminates, and obtains copper Fe compound type SAPO-34 molecular sieve catalyst.
2. the preparation method of copper Fe compound type SAPO-34 molecular sieve catalyst as claimed in claim 1, is characterized in that: described
Iron salt is the one or two kinds of in solubility ferric nitrate, iron chloride；And mantoquita is the copper nitrate of solubility, Schweinfurt green, sulphuric acid
One or both in copper, copper chloride, copper acetate.
3. a preparation method for copper Fe compound type SAPO-34 molecular sieve catalyst, is characterized in that this preparation method includes following
Step:
A2, boehmite is sufficiently stirred in deionized water, is subsequently adding phosphoric acid by complete for boehmite peptization, treats glue
It is dissolved complete rear addition silicon dioxide and mantoquita stirs, be subsequently adding triethylamine and TEPA and stir, filling after stirring
Entering crystallization in reactor, gained is CuSAPO-34 molecular sieve；
B2, add iron salt in deionized water, obtain iron salt solutions so that in iron salt solutions, the mass fraction of iron ion is 0.5%
~ 3%, by the ammonia that dropping mass fraction is 15% ~ 25%, the pH value of solution is regulated to 1 ~ 6；
C2, by [Fe3+] it is 0.5 ~ 3:1 by metal salt solution with the CuSAPO-of one-step synthesis method with the mol ratio of [CuSAPO-34]
Stirring 1 ~ 3h after 34 molecular sieve mixing, 60 ~ 85 DEG C of water-bath 0.5 ~ 4h of constant temperature, obtain solid product subsequently；
D2, by the solid product of gained through deionized water wash, until cleaning mixture is to neutral；
E2, solid product is put in 80 ~ 150 DEG C of baking ovens be dried 5 ~ 12 hours, subsequently with the programming rate liter of 3 ~ 10 DEG C/min
Temperature was to 400 ~ 650 DEG C of roastings 2 ~ 10 hours, and roasting terminates, and obtains copper Fe compound type SAPO-34 molecular sieve catalyst.
4. the preparation method of copper Fe compound type SAPO-34 molecular sieve catalyst as claimed in claim 3, is characterized in that: described
Iron salt is the one or two kinds of in solubility ferric nitrate, iron chloride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109499607A (en) * | 2018-11-13 | 2019-03-22 | 中节能万润股份有限公司 | A kind of copper and iron composite honeycomb coating type denitrating catalyst and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008118434A1 (en) * | 2007-03-26 | 2008-10-02 | Pq Corporation | Novel microporous crystalline material comprising a molecular sieve or zeolite having an 8-ring pore opening structure and methods of making and using same |
| CN102614910A (en) * | 2012-03-16 | 2012-08-01 | 北京工业大学 | Ammonia-selective preparation method of SAPO-34 supported Cu-Fe catalyst for catalytically removing NOx |
| CN103818927A (en) * | 2014-02-20 | 2014-05-28 | 无锡威孚环保催化剂有限公司 | One-step method for synthesizing copper-containing CHA type molecular sieve with high hydro-thermal stability |
| CN104307564A (en) * | 2014-09-09 | 2015-01-28 | 天津大学 | Auxiliary agent doped Cu-SAPO-34 catalyst, preparation method and applications thereof |
| CN105214720A (en) * | 2015-10-14 | 2016-01-06 | 无锡威孚环保催化剂有限公司 | For motor-vehicle tail-gas NO xthe preparation method of the molecular sieve catalyst eliminated |
-
2016
- 2016-07-08 CN CN201610539337.9A patent/CN106215974B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008118434A1 (en) * | 2007-03-26 | 2008-10-02 | Pq Corporation | Novel microporous crystalline material comprising a molecular sieve or zeolite having an 8-ring pore opening structure and methods of making and using same |
| CN102614910A (en) * | 2012-03-16 | 2012-08-01 | 北京工业大学 | Ammonia-selective preparation method of SAPO-34 supported Cu-Fe catalyst for catalytically removing NOx |
| CN103818927A (en) * | 2014-02-20 | 2014-05-28 | 无锡威孚环保催化剂有限公司 | One-step method for synthesizing copper-containing CHA type molecular sieve with high hydro-thermal stability |
| CN104307564A (en) * | 2014-09-09 | 2015-01-28 | 天津大学 | Auxiliary agent doped Cu-SAPO-34 catalyst, preparation method and applications thereof |
| CN105214720A (en) * | 2015-10-14 | 2016-01-06 | 无锡威孚环保催化剂有限公司 | For motor-vehicle tail-gas NO xthe preparation method of the molecular sieve catalyst eliminated |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499607A (en) * | 2018-11-13 | 2019-03-22 | 中节能万润股份有限公司 | A kind of copper and iron composite honeycomb coating type denitrating catalyst and its preparation method and application |
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