CN107126973A - A kind of in-situ synthetic method of catalyst of CuFe SAPO 34 and its application - Google Patents
A kind of in-situ synthetic method of catalyst of CuFe SAPO 34 and its application Download PDFInfo
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- cufe
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 8
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- 241000269350 Anura Species 0.000 title abstract 5
- 238000000034 method Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 229910001868 water Inorganic materials 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000012452 mother liquor Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 41
- 239000010949 copper Substances 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910002706 AlOOH Inorganic materials 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 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 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- 229940079721 copper chloride Drugs 0.000 claims description 2
- 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
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229940108928 copper Drugs 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 235000011007 phosphoric acid Nutrition 0.000 abstract description 5
- 230000001846 repelling effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 abstract description 3
- 229910021485 fumed silica Inorganic materials 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 10
- 231100000572 poisoning Toxicity 0.000 description 8
- 230000000607 poisoning effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000006308 propyl amino group Chemical group 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004888 n-propyl amino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of in-situ synthetic method of catalyst of CuFe SAPO 34 and its application, belong to catalysis technical field.The inventive method comprises the following steps：Boehmite is added in deionized water and is stirred dissolving, orthophosphoric acid and fumed silica is then added, mantoquita and TEPA are added after mixing, Fe salt and n-propylamine are added after being sufficiently stirred for；It will stir after the completion of complete gel is fitted into crystallization in hydrothermal reaction kettle, crystallization and be cooled to room temperature, solid crystallized product will be separated with mother liquor, it is washed with deionized to neutrality, dry, be then calcined in atmosphere, obtain the small pore molecular sieve catalysts of CuFe SAPO 34.The present invention prepares the catalyst of CuFe SAPO 34 using one-step synthesis, by preferred Fe load capacity, significantly improves the catalytic performance and low temperature water repelling property of the catalyst of Cu SAPO 34.
Description
Technical field
The present invention relates to a kind of in-situ synthetic method of CuFe-SAPO-34 catalyst and its application, belong to catalysis technique neck
Domain.
Background technology
NOxThe atmosphere polluting problems such as haze, acid rain, photochemical fog can be caused, be atmosphere pollution important at present,
It is the key object of the current China's prevention and control of air pollution of China.The combustion of fossil fuel that people's industrial production and life activity are brought
It is nitrogen oxides (NOx) main source.In artificial source NOxIn discharge, using coal-fired plant flue gas as the stationary source of representative and diesel oil
Tail gas is the NO of the moving source of representativexOccupy about 60% discharge share.With the raising of national Abgasgesetz standard, move
Dynamic source NOxThe processing method that emission compliance need to be combined using internal purification technology and post-processing technology.Wherein post-processing approach
Improvement is the major way for the standard that reply is improved constantly.SCR technology (Selective in post processing
Catalytic Reduction, SCR) there are removal efficiency height, low cost and other advantages, obtain more concern.SCR technology is just
Refer under conditions of catalyst is present, NH is sprayed into flue gas3, urea or other reducing agents, make its optionally with NOxInstead
N should be generated2, without with O2Generation non-selective oxidation, so as to reach reduction NOxReduction temperature, raising NOxThe mesh of purification efficiency
's.The core of SCR technology is the outstanding catalyst of catalytic performance.
At present V is still in the catalyst of China's wide popularization and application2O5-WO3(MoO3)/TiO2.The catalyst is extensive
Applied to stationary source coal-fired flue gas denitration, and it is also introduced into exhaust gas from diesel vehicle control field.But the catalyst system use
Still there are many problems in diesel car tail gas refining.For qualified discharge, in moving source exhaust treatment system, SCR processing systems are past
It is combined toward needs with particulate matter trap (DPF).It is thus desirable to which SCR catalyst can bear the high temperature brought during dpf regeneration
(being higher than 700 DEG C) and the environment of high humility, i.e. catalyst needs to have excellent hydrothermal stability.But V2O5-WO3(MoO3)/
TiO2Volatilization and the carrier TiO of vanadium can occur more than 600 DEG C for catalyst2Phase transformation, so the catalyst be not suitable for temperature compared with
High motor-driven vehicle gas disposal, it is impossible to meet tomorrow requirement.The bio-toxicity of other vanadium also limit its use.Other researchs
More ripe is the different degrees of presence temperature of catalyst series such as Cu bases or Fe bases prepared by carrier with ZSM-5, beta and Y etc.
Spend action pane narrow, the problems such as poor and anti-HC poisoning capabilities of hydrothermal stability are poor.Therefore, the NH of environment-friendly high-efficiency is developed3- SCR is urged
Agent is very urgent.
Small pore molecular sieve catalyst is current NH3The study hotspot in-SCR fields, wherein the Cu-SAPO- with CHA structure
34 catalyst are the representatives of such molecular sieve catalyst, and such catalyst is provided simultaneously with high activity, high N2It is selective and excellent
Hydrothermal stability.But such catalyst is more sensitive to the environment of cold aqueous, and sulfur poisoning resistance is poor, to practical application
It is unfavorable.So, further improve the catalyst and be very important.
Cu and Fe are loaded on SAPO-34 carriers with liquid-phase ion exchange by 2012100717231 patent disclosure
Preparing compound small pore molecular sieve catalyst is used for NOx catalytic purifications.But this method complex steps, it is necessary to repeatedly load, and gold
Belong to load capacity to be difficult to control.The low temperature water repelling property and sulfur poisoning resistance of gained catalyst are also without relevant report.
The content of the invention
In order to solve the above problems, an object of the present invention is that provide one kind prepares CuFe- by in-situ synthesis
The preparation method of SAPO-34 catalyst, catalyst is made by hydrothermal synthesis method, is small pore molecular sieve class catalyst.The present invention
Method it is simple to operation, gained catalyst has excellent NH3- SCR catalytic performances, can be used for moving source NH3- SCR denitration
Process.In addition, the catalyst of the selective catalyst reduction of nitrogen oxides prepared, operation temperature window is wide, with excellent
N2Generation selectivity and hydrothermal stability, are highly suitable for the purification of nitrogen oxides in exhaust gas from diesel vehicle.
The in-situ synthesis method for preparing CuFe-SAPO-34 catalyst of the present invention, be by silicon source, water, phosphorus source, silicon source,
Cu sources, TEPA, and source of iron are mixed evenly, and then add template, continue to stir；Complete gel dress will be stirred
Enter crystallization in hydrothermal reaction kettle, crystallization is cooled down after terminating；Solid crystallized product is separated with mother liquor, washs, dry, roast
Burn, that is, obtain CuFe-SAPO-34 small pore molecular sieve catalysts.
In one embodiment, source of aluminium can be boehmite AlOOH, alundum (Al2O3), sodium metaaluminate etc..
In one embodiment, phosphorus source is phosphoric acid.
In one embodiment, the silicon source is silica, Ludox etc..
In one embodiment, the Cu sources are Cu salt.
In one embodiment, the Cu salt is copper sulphate, copper nitrate, copper acetate, copper chloride, copper carbonate, cupric oxide
Any one in or two or more combinations.
In one embodiment, the source of iron is molysite.
In one embodiment, the molysite is ferric nitrate, iron chloride, ferrous sulfate, ferric sulfate, frerrous chloride, lemon
Any one in lemon acid iron etc. or two or more combinations.
In one embodiment, the template is n-propylamine (C3H9N), diethylamine, triethylamine, tetraethylamine hydroxide
Any one in or two or more combinations.
In one embodiment, methods described, specifically includes following steps：
(1) boehmite is added in deionized water and stirred；
(2) phosphoric acid is added, is stirred；
(3) fumed silica is added to be stirred；
(4) after above-mentioned medicine is well mixed, Cu salt and TEPA are added；
(5) after being sufficiently mixed, molysite and n-propylamine are added, continues to stir.
(6) complete gel will be stirred and is fitted into crystallization in hydrothermal reaction kettle, crystallization is cooled to room temperature after terminating.Will be solid
Body crystallized product is separated with mother liquor, is washed with deionized to neutrality, is dried, is then calcined, that is, obtains in air atmosphere
CuFe-SAPO-34 small pore molecular sieve catalysts.
In one embodiment, methods described control silicon source, phosphorus source, silicon source, water, Cu sources, TEPA, source of iron,
The mol ratio of template is (0.75-1.25)：(0.75-1.25)：(0.4-0.7)：(70-80)：(0.01-3.5)：(0.01-
3.5)：(0.001-0.1)：(0.01-3.5).
In one embodiment, methods described control silicon source, phosphorus source, silicon source, water, Cu sources, TEPA, source of iron,
The mol ratio of template is 1：1：0.57：77.17：0.12：0.12：(0.019-0.076)：3.38.
In one embodiment, source of aluminium, phosphorus source, silicon source, water, Cu sources, TEPA, source of iron, template point
Wei not AlOOH, H3PO4、SiO2、H2O, Cu salt, TEPA, Fe salt and n-propylamine.
In one embodiment, AlOOH, H3PO4、SiO2、H2O, Cu salt, TEPA, Fe salt and n-propylamine rub
You are than being 1：1：0.57：77.17：0.12：0.12：0.057：3.38.
In one embodiment, the temperature of crystallization be 150-200 DEG C, such as 150,155,160,165,170,175,
180th, 185,190,195 or 200 DEG C.
In one embodiment, the time of the crystallization be 24-72h, such as 30,35,40,45,50,55,60,
65、72h。
In one embodiment, the time of the crystallization is 72h.
In one embodiment, the washing is to be washed with water to neutrality.
In one embodiment, the temperature of the drying be 80-120 DEG C, such as 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120
℃。
In one embodiment, the temperature of the drying is 100 DEG C.
In one embodiment, the time of the drying is 3-16 hours, such as 3h, 5h, 6h, 8h, 10h, 12h, 16h.
In one embodiment, the time of the drying is 12h.
In one embodiment, the roasting is calcined in air atmosphere.
In one embodiment, the temperature of the roasting be 550-800 DEG C, such as 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C,
800℃。
In one embodiment, the temperature of the roasting is 600 DEG C.
In one embodiment, the time of the roasting is 3-10 hours, such as 3h, 5h, 6h, 8h, 10h.
In one embodiment, the time of the roasting is 6h.
In one embodiment, the heating rate of the roasting be 0.5-5 DEG C/min, for example, 0.5,1,1.5,2,
2.5、3、3.5、4、4.5、5℃/min。
In one embodiment, the roasting heating rate is 1 DEG C/min.
In one embodiment, methods described specifically includes following steps：Boehmite is added in deionized water
It is stirred, then adds orthophosphoric acid and fumed silica, mantoquita and TEPA is added after mixing, is sufficiently stirred for
Fe salt and n-propylamine are added afterwards；It will stir after the completion of complete gel is fitted into crystallization in hydrothermal reaction kettle, crystallization and be cooled to
Room temperature, solid crystallized product is separated with mother liquor, is washed with deionized to neutrality, is dried, be then calcined, obtain in atmosphere
CuFe-SAPO-34 small pore molecular sieve catalysts；Wherein control AlOOH, H3PO4、SiO2、H2O, Cu salt, TEPA, Fe salt
Mol ratio with n-propylamine is 1：1：0.57：77.17：0.12：0.019-0.076：3.38.Using catalyst tool obtained by the program
There is excellent catalytic activity, it has the conversion rate of NOx higher than 80% in 300-500 DEG C, and significantly improves Cu-
SAPO-34 low temperature water repelling property.
Second object of the present invention is to provide the CuFe-SAPO-34 small pore molecular sieves prepared according to the method described above
Catalyst.
Third object of the present invention is to provide the application of the CuFe-SAPO-34 small pore molecular sieve catalysts.
In one embodiment, the application is to be used for catalyst nox.
In one embodiment, the application is to be used for NH3- SCR reacts.
In one embodiment, the application is nitrogen oxides in catalysis reduction exhaust gas from diesel vehicle.
Beneficial effects of the present invention：
(1) this method prepares CuFe-SAPO-34 small pore molecular sieve catalysts using in-situ synthesis, and further passes through
The input amount of Fe salt is controlled to control the load capacity of Fe salt, to obtain NH3Point of-SCR catalytic activity and water resistant excellent in stability
Sub- sieve catalyst；The preparation method of the CuFe-SAPO-34 is one-step synthesis, compared to the ion exchange in solution used at present
Method is more easy and effective, without multistep ion-exchange step, economizes on resources.
(2) this method prepares gained catalyst using the cooperative effect between Cu and Fe, opens up the temperature window of catalyst
The raising of width, particularly high temperature section activity is more notable, is more applicable for diesel car tail gas refining.
(3) catalyst prepared by this method improves its low temperature water resistant ability.
(4) catalyst prepared by this method improves sulfur poisoning resistance.
(5) catalyst of the invention is prepared using nontoxic component, and health and ecological environment will not be caused harm；System
Preparation Method is simple to operation.
Brief description of the drawings
CuFe-SAPO-34 and Cu-SAPO-34 catalyst activity and water resistant poisoning capability ratio that Fig. 1 is prepared for the present invention
Compared with；
The change for the CuFe-SAPO-34 and Cu-SAPO-34 catalyst sulfur poisoning resistances that Fig. 2 is prepared for the present invention.
Specific embodiment
In the present invention, following method is taken in the evaluation of catalyst：
CuFe-SAPO-34 molecular sieve catalysts are taken, are placed on activity rating fixed bed reactors, simulated exhaust composition
For 500ppm NH3, 500ppm NO, 5vol%O2, N2For Balance Air, total flow is 500mL/min, and reaction velocity is
400000h-1。
Here is that the present invention is specifically described.
Embodiment 1
Using boehmite AlOOH as silicon source, silica (SiO2) it is silicon source, phosphoric acid (H3PO4) it is phosphorus source, Cu-TEPA
For Cu sources, Fe (NO3)3·9H2O is source of iron, and each raw material is mixed, and then adds n-propylamine (C3H9N it is) template, is stirred overnight
Until stirring；Solution is put into reactor again, reactor is put into crystallization 3d in 180 DEG C of baking oven；Question response kettle fills
Divide after cooling, stirring, which is stood, simultaneously filters out suction filtration after impurity, and the baking oven 3h that the sample after filtering is put into 105 DEG C is baked to；Again
The sample of drying is put into Muffle furnace, 600 DEG C of roasting 6h are risen to 1 DEG C/min programming rate, one-step synthesis legal system is obtained
Standby CuFe-SAPO-34 catalyst.Wherein, AlOOH, H are controlled3PO4、SiO2、H2O, Cu salt, TEPA, Fe salt and just
The mol ratio of propylamine is 1：1：0.57：77.17：0.12：：0.12：0.057：3.38.
Control：Without Fe salt, according to above-mentioned preparation method, Cu-SAPO-34 catalyst can be made.
Before and after investigation addition Fe salt, the low temperature water resistant capacity variation of catalyst, by catalyst containing 10%H2O air
In atmosphere, through 70 DEG C of aging 16h, the catalyst performance change before and after detection aging.Fig. 1 provides catalyst performance before and after the addition of Fe salt
Can change
From figure 1 it appears that the temperature window of CuFe-SAPO-34 catalyst is wider, can be in the range of 250-550 DEG C
70% conversion rate of NOx is remained above, most highly active can reach 90.3%.And the temperature window for compareing Cu-SAPO-34 is narrower,
It is only capable of being remained above 60% conversion rate of NOx in the range of 250-350 DEG C, most highly active can reach 78.6%.
In addition, CuFe-SAPO-34 is after 70 DEG C of aging 16h, catalyst can be still remained above in the range of 300-500 DEG C
50% conversion rate of NOx.And Cu-SAPO-34 is compareed after the processing of identical aging condition, kept only in the range of 300-450 DEG C
Conversion rate of NOx more than 30%.
By data above, it is known that this method not only improves the activity of catalyst, its low temperature water repelling property is also significantly improved.
Fig. 2 provides the situation of the sulfur poisoning resistance of catalyst before and after Fe is added, it is known that the CuFe-SAPO- after sulfur poisoning
34 catalyst can still remain larger than 60% conversion ratio at 350-500 DEG C, and highest conversion rate of NOx is 81.5%.But Cu-SAPO-
34 catalyst only remain larger than 60% conversion ratio at 400-500 DEG C, and highest conversion rate of NOx is 62.9%.
Embodiment 2
The present embodiment has investigated the performance of the CuFe-SAPO-34 catalyst obtained under different Fe salt additions.
The preparation method of catalyst：Fe dosage is adjusted, AlOOH, H is controlled3PO4、SiO2、H2O, Cu salt, four ethene five
The mol ratio of amine, Fe salt and n-propylamine is respectively A (1：1：0.57：77.17：0.12：0.12：0.0095：3.38)、B(1：1：
0.57：77.17：0.12：0.12：0.019：3.38)、C(1：1：0.57：77.17：0.12：0.12：0.029：3.38)、D(1：
1：0.57：77.17：0.12：0.12：0.043：3.38).Remaining is same as Example 1.
The CuFe-SAPO-34 catalyst prepared, catalytic performance at different temperatures is as shown in table 1.
The catalytic performance of the catalyst obtained under the difference Fe additions of table 1
Embodiment 3
The present embodiment has investigated the performance of the CuFe-SAPO-34 catalyst obtained under different crystallization temperatures.
Control AlOOH, H3PO4、SiO2、H2O, Cu salt, TEPA, the mol ratio of Fe salt and n-propylamine are 1：1：
0.57：77.17：0.12：：0.12：0.057：3.38, crystallization temperature is respectively 150 DEG C, 200 DEG C, and remaining is same as Example 1.
The performance of the CuFe-SAPO-34 catalyst prepared is as shown in table 2.
The catalytic performance of the catalyst obtained under the different crystallization temperatures of table 2
Although the present invention is disclosed as above with preferred embodiment, it is not limited to the present invention, any to be familiar with this skill
The people of art, without departing from the spirit and scope of the present invention, can do various changes and modification, therefore the protection model of the present invention
Enclose being defined of being defined by claims.
Claims (10)
1. a kind of method that in-situ synthesis prepares CuFe-SAPO-34 catalyst, it is characterised in that methods described be by silicon source,
Phosphorus source, silicon source, water, Cu sources, TEPA, and source of iron are mixed evenly, and then add template, continue to stir；It will stir
Mix complete gel and be fitted into crystallization in hydrothermal reaction kettle, crystallization is cooled down after terminating；Solid crystallized product is separated with mother liquor,
Washing, dry, roasting, that is, obtain CuFe-SAPO-34 small pore molecular sieve catalysts.
2. according to the method described in claim 1, it is characterised in that methods described control silicon source, phosphorus source, silicon source, water, Cu sources,
TEPA, source of iron, the mol ratio of template are (0.75-1.25)：(0.75-1.25)：(0.4-0.7)：(70-80)：
(0.01-3.5)：(0.01-3.5)：(0.001-0.1)：(0.01-3.5).
3. according to the method described in claim 1, it is characterised in that methods described control silicon source, phosphorus source, silicon source, water, Cu sources,
TEPA, source of iron, the mol ratio of template are 1：1：0.57：77.17：0.12：0.12：(0.019-0.076)：3.38.
4. according to the method described in claim 1, it is characterised in that source of aluminium is boehmite AlOOH, alundum (Al2O3)
Or sodium metaaluminate.
5. according to the method described in claim 1, it is characterised in that the source of iron is molysite, such as ferric nitrate, iron chloride, sulphur
Any one in sour ferrous iron, ferric sulfate, frerrous chloride, ironic citrate or two or more combinations.
6. according to the method described in claim 1, it is characterised in that the Cu sources are Cu salt, such as copper sulphate, copper nitrate, vinegar
Any one in sour copper, copper chloride, copper carbonate, cupric oxide or two or more combinations.
7. according to the method described in claim 1, it is characterised in that the temperature of crystallization is 150-200 DEG C.
8. the CuFe-SAPO-34 catalyst prepared according to any methods described of claim 1~7.
9. the application of CuFe-SAPO-34 catalyst described in claim 8.
10. application according to claim 9, it is characterised in that for NH3- SCR reacts.
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