CN109529916A - A kind of preparation method of the molecular sieve catalyst for NH3-SCR denitrating flue gas - Google Patents
A kind of preparation method of the molecular sieve catalyst for NH3-SCR denitrating flue gas Download PDFInfo
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- CN109529916A CN109529916A CN201811596424.3A CN201811596424A CN109529916A CN 109529916 A CN109529916 A CN 109529916A CN 201811596424 A CN201811596424 A CN 201811596424A CN 109529916 A CN109529916 A CN 109529916A
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- molecular sieve
- scandium
- neodymium
- flue gas
- sieve catalyst
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 96
- 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 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000003546 flue gas Substances 0.000 title claims abstract description 36
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 51
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000001802 infusion Methods 0.000 claims abstract description 7
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract 10
- 150000003325 scandium Chemical class 0.000 claims description 29
- 150000001206 Neodymium Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000009938 salting Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- MIJKIIBNAPRONL-UHFFFAOYSA-N acetic acid;neodymium Chemical compound [Nd].CC(O)=O MIJKIIBNAPRONL-UHFFFAOYSA-N 0.000 claims description 4
- OQRMRSDZEJMEHR-UHFFFAOYSA-N acetic acid;scandium Chemical compound [Sc].CC(O)=O OQRMRSDZEJMEHR-UHFFFAOYSA-N 0.000 claims description 4
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 4
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- ZCNBOEGXFWYXEO-UHFFFAOYSA-N scandium Chemical compound [Sc].[Sc] ZCNBOEGXFWYXEO-UHFFFAOYSA-N 0.000 description 39
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 7
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B01J35/61—
-
- 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
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention belongs to catalytic denitration technical fields, and in particular to one kind is used for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, using ZSM-5 molecular sieve as carrier, using scandium, neodymium metallic element as active component, scandium, neodymium metallic element are supported on ZSM-5 molecular sieve by infusion process, wherein, the mass percent of scandium and ZSM-5 molecular sieve is 16-24%, and the molar ratio of neodymium and scandium is 0.3-0.5.Molecular sieve catalyst of the present invention effectively increases the catalytic activity of molecular sieve catalyst, by toxic NOxIt is catalytically conveted to nontoxic N2And H2O；The anti-SO of molecular sieve catalyst also can be improved2Poisoning performance can be applied in vehicle exhaust low temperature SCR denitration system.
Description
[technical field]
The invention belongs to catalytic denitration technical fields, and in particular to one kind is used for NH3The molecular sieve of-SCR denitrating flue gas is urged
The preparation method of agent.
[background technique]
NOxIt mainly include NO and NO2, it will form acid rain, photochemical fog and gray haze etc. by complicated chemical reaction, it is right
Human health and ecological environment cause grave danger, are one of main atmosphere pollutions.NOxArtificial source be divided into stationary source and
Moving source, stationary source refer to the tail gas of coal-burning boiler, industrial furnace etc.；Moving source refers to motor-vehicle tail-gas, especially exhaust gas from diesel vehicle.
In recent years, diesel vehicle NOxEmission control is of increasing concern.Ammonia selective catalyst reduction of nitrogen oxides technology is deposited in oxygen
Under the conditions, redox reaction occurs under the action of catalyst for the NO in reducing agent ammonia and flue gas, makes NO and NH3Conversion
For harmless N2And H2O.The technology is internationally recognized most mature, the commercialization denitration technology that is most widely used at present.For
NH3- SCR catalysis technique, catalyst are its core and key, currently, being provided simultaneously with wide in deamination catalyst technical field
Active temperature windows, high catalytic activity and anti-SO2Poisoning performance is the hot and difficult issue of research.
[summary of the invention]
In view of above content, it is necessary to provide a kind of for NH3The preparation side of the molecular sieve catalyst of-SCR denitrating flue gas
Method, molecular sieve catalyst made of the preparation method effectively increases the catalytic activity of molecular sieve catalyst, by toxic NOxIt urges
Change is converted into nontoxic N2And H2O；The anti-SO of molecular sieve catalyst also can be improved2Poisoning performance can be applied low in vehicle exhaust
In warm SCR denitration system.
In order to achieve the above objectives, the technical scheme adopted by the invention is that:
One kind being used for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, using ZSM-5 molecular sieve as load
Scandium, neodymium metallic element are supported on ZSM-5 molecular sieve using scandium, neodymium metallic element as active component by infusion process by body,
Wherein, the quality of scandium is the 16-24% of ZSM-5 molecular sieve, and the molar ratio of neodymium and scandium is 0.3-0.5；Specifically includes the following steps:
(1) ratio for being 0.3-0.5 in 16-24% and the molar ratio of neodymium and scandium that the quality of scandium is ZSM-5 molecular sieve, point
Also known as take soluble scandium salts, soluble neodymium salt and ZSM-5 molecular sieve；Soluble scandium salts, soluble neodymium salt are separately added into two parts
It in the identical ethanol solution of volume, and is sufficiently stirred, respectively obtains soluble scandium salts solution and soluble neodymium salting liquid；
(2) ZSM-5 molecular sieve is placed in baking oven after carrying out drying and processing and is taken out, be then cooled to room temperature addition step to it
Suddenly in the soluble scandium salts solution that (1) obtains, and dispersing agent is added, system A is obtained after stirring, system A is placed in ultrasonic reaction
It is ultrasonically treated in device, obtains system B；
(3) the soluble neodymium salting liquid that step (1) obtains is added in the system B that step (2) obtain, then at room temperature
50-70min is stirred, system C is obtained；
(4) the system C for obtaining step (3), which is dried, obtains powder, and powder is then roasted 4-5h, then natural cooling
It obtains after to room temperature for NH3The molecular sieve catalyst of-SCR denitrating flue gas.
In the present invention, further instruction, solubility scandium salts described in step (1) is in acetic acid scandium or scandium nitrate
The mixture that one or both is mixed with arbitrary proportion.
In the present invention, further instruction, solubility neodymium salt described in step (1) is in neodymium nitrate and acetic acid neodymium
The mixture that one or both is mixed with arbitrary proportion.
In the present invention, further instruction, the temperature of drying described in step (2) are 80-90 DEG C, drying and processing when
Between be 3.5-4.5h.
In the present invention, further instruction, dispersing agent described in step (2) are polyvinylpyrrolidone, the poly- second
The volume ratio of alkene pyrrolidone and soluble scandium salts solution is 1-2:6-8.
In the present invention, further instruction, the time of step (2) described stirring are 25-65min.
In the present invention, further instruction, the time of step (2) described ultrasonic treatment are 50-80min；The frequency of ultrasound
Rate is 30-40kHz.
In the present invention, further instruction, the temperature condition of drying process described in step (4) are 100-120 DEG C, are done
The dry time is 11-13h.
In the present invention, further instruction, the temperature of roasting described in step (4) are 400-650 DEG C.
In the present invention, ZSM-5 molecular sieve is due to SCR activity with higher and wider active temperature windows, Chang Ying
For in SCR denitration technology, meanwhile, ZSM-5 molecular sieve Si/Al ratio with higher and bone valence are electrical, therefore have good
Structural stability, acid resistance, heat resistance and water resistant thermal stability, ensure that the performance of molecular sieve catalyst using it as carrier, separately
Outside, there is ZSM-5 molecular sieve high specific surface area and unique cellular structure can effectively divide as catalyst carrier
Dissipate active component scandium, neodymium metallic element, in addition molecular sieve itself have certain silica alumina ratio affect scandium, neodymium element oxidation also
Originality energy, meanwhile, in the present invention, scandium, neodymium and ZSM-5 molecular sieve are strictly matched, and have the function of synergy, thus effectively
Improve catalytic activity.
Furthermore the addition of neodymium can widen active temperature windows, and not influence the N of catalyst2Selectivity；The addition of neodymium may be used also
The formation of surface sulfate species is effectively reduced, and then improves the anti-SO of molecular sieve catalyst2Poisoning performance.
Scandium, neodymium metallic element are supported on ZSM-5 molecular sieve by infusion process, process flow is simple, is readily produced.
The present invention is by adopting the above scheme, have the following beneficial effects:
1. the present invention combines the distinctive characteristic of ZSM-5 molecular sieve, scandium, the load of neodymium metallic element are loaded according to a certain percentage
Thereon, it so that the ratio of scandium, neodymium and ZSM-5 molecular sieve reaches special value each other with synergistic function, effectively mentions
The high catalytic activity of molecular sieve catalyst, by toxic NOxIt is catalytically conveted to nontoxic N2And H2O can be applied in car tail
In gas low temperature SCR denitration system, there is excellent catalytic activity, NO within the temperature range of 150-600 DEG CxConversion ratio >
90%.
2. the anti-SO of molecular sieve catalyst can be improved due to the addition of neodymium in the present invention2Poisoning performance, obtained catalyst
Containing SO2Still there is preferable low temperature NH after reacting 3h in atmosphere3- SCR performance, NOxConversion ratio is 75% or more.
[specific embodiment]
It is a kind of for NH the present invention provides providing3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, to make
The purpose of the present invention, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that
The specific embodiments described herein are merely illustrative of the present invention, is not intended to limit the present invention.
Embodiment 1
It is provided in this embodiment to be used for NH3The molecular sieve catalyst of-SCR denitrating flue gas the preparation method is as follows:
One kind being used for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, using ZSM-5 molecular sieve as load
Scandium, neodymium metallic element are supported on ZSM-5 molecular sieve using scandium, neodymium metallic element as active component by infusion process by body,
Wherein, the quality of scandium is the 16% of ZSM-5 molecular sieve, and the molar ratio of neodymium and scandium is 0.3；Specifically includes the following steps:
(1) ratio for being 0.3 in 16% and the molar ratio of neodymium and scandium that the quality of scandium is ZSM-5 molecular sieve, weighs respectively
Soluble scandium salts, soluble neodymium salt and ZSM-5 molecular sieve, the solubility scandium salts are selected from acetic acid scandium, and the solubility neodymium salt is
Neodymium nitrate；Soluble scandium salts, soluble neodymium salt are separately added into the identical ethanol solution of two parts of volumes, and sufficiently stirred
It mixes, respectively obtains soluble scandium salts solution and soluble neodymium salting liquid；
(2) ZSM-5 molecular sieve is placed in the baking oven that temperature is 80 DEG C after carrying out drying and processing 3.5h and is taken out, then to it
It is cooled to room temperature and is added in step (1) obtained soluble scandium salts solution, and polyvinylpyrrolidone is added as dispersing agent,
In, the volume ratio of the polyvinylpyrrolidone and soluble scandium salts solution is 1:6, system A is obtained after stirring 25min, by body
It is that A is placed in ultrasonic reactor and carries out ultrasonic treatment 50min, ultrasonic frequency is 30kHz, obtains system B；
(3) the soluble neodymium salting liquid that step (1) obtains is added in the system B that step (2) obtain, then at room temperature
50min is stirred, system C is obtained；33 starch
(4) the system C that step (3) obtains is placed under the conditions of 100 DEG C of temperature after being dried 11h and obtains powder, connect
Powder is placed under conditions of 400 DEG C roast 4h, then cooled to room temperature after obtain for NH3- SCR denitrating flue gas
Molecular sieve catalyst.
Embodiment 2
It is provided in this embodiment to be used for NH3The molecular sieve catalyst of-SCR denitrating flue gas the preparation method is as follows:
One kind being used for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, using scandium, neodymium metallic element as live
Property component, scandium, neodymium metallic element are supported on ZSM-5 molecular sieve by infusion process, wherein the quality of scandium scandium is ZSM-5 point
The molar ratio of the 20% of son sieve, neodymium and scandium is 0.4；Specifically includes the following steps:
(1) ratio for being 0.4 in 20% and the molar ratio of neodymium and scandium that the quality of scandium is ZSM-5 molecular sieve, weighs respectively
Soluble scandium salts, soluble neodymium salt and ZSM-5 molecular sieve, the solubility scandium salts are selected from scandium nitrate, and the solubility neodymium salt is
Acetic acid neodymium；Soluble scandium salts, soluble neodymium salt are separately added into the identical ethanol solution of two parts of volumes, and sufficiently stirred
It mixes, respectively obtains soluble scandium salts solution and soluble neodymium salting liquid；
(2) ZSM-5 molecular sieve is placed in the baking oven that temperature is 85 DEG C after carrying out drying and processing 4h and is taken out, then to its drop
It is added in step (1) obtained soluble scandium salts solution after to room temperature, and polyvinylpyrrolidone is added as dispersing agent,
In, the volume ratio of the polyvinylpyrrolidone and soluble scandium salts solution is 1.5:7, obtains system A after stirring 35min, will
System A, which is placed in ultrasonic reactor, carries out ultrasonic treatment 75min, and ultrasonic frequency is 35kHz, obtains system B；
(3) the soluble neodymium salting liquid that step (1) obtains is added in the system B that step (2) obtain, then at room temperature
60min is stirred, system C is obtained；
(4) the system C that step (3) obtains is placed under the conditions of 110 DEG C of temperature after being dried 12h and obtains powder, connect
Powder is placed under conditions of 500 DEG C roast 4.5h, then cooled to room temperature after obtain for NH3- SCR denitrating flue gas
Molecular sieve catalyst.
Embodiment 3
It is provided in this embodiment to be used for NH3The molecular sieve catalyst of-SCR denitrating flue gas the preparation method is as follows:
One kind being used for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, using ZSM-5 molecular sieve as load
Scandium, neodymium metallic element are supported on ZSM-5 molecular sieve using scandium, neodymium metallic element as active component by infusion process by body,
Wherein, the quality of scandium is the 24% of ZSM-5 molecular sieve, and the molar ratio of neodymium and scandium is 0.5；Specifically includes the following steps:
(1) ratio for being 0.5 in 24% and the molar ratio of neodymium and scandium that the quality of scandium is ZSM-5 molecular sieve, weighs respectively
Soluble scandium salts, soluble neodymium salt and ZSM-5 molecular sieve, the solubility scandium salts are selected from acetic acid scandium and scandium nitrate with arbitrary proportion
Mixed mixture, the solubility neodymium salt are the mixture that neodymium nitrate and acetic acid neodymium are mixed with arbitrary proportion；By soluble scandium
Salt, soluble neodymium salt are separately added into the identical ethanol solution of two parts of volumes, and are sufficiently stirred, and respectively obtain soluble scandium
Salting liquid and soluble neodymium salting liquid；
(2) ZSM-5 molecular sieve is placed in baking oven at a temperature of 90 °C after carrying out drying and processing 4.5h and is taken out, then to it
It is cooled to room temperature and is added in step (1) obtained soluble scandium salts solution, and polyvinylpyrrolidone is added as dispersing agent,
In, the volume ratio of the polyvinylpyrrolidone and soluble scandium salts solution is 2:8, system A is obtained after stirring 65min, by body
It is that A is placed in ultrasonic reactor and carries out ultrasonic treatment 80min, ultrasonic frequency is 40kHz, obtains system B；
(3) the soluble neodymium salting liquid that step (1) obtains is added in the system B that step (2) obtain, then at room temperature
70min is stirred, system C is obtained；
(4) the system C that step (3) obtains is placed under the conditions of 120 DEG C of temperature after being dried 13h and obtains powder, connect
Powder is placed under conditions of 650 DEG C roast 4-5h, then cooled to room temperature after obtain for NH3-SCR denitrating flue gas
Molecular sieve catalyst.
Comparative example 1
What this comparative example provided is used for NH3The molecular sieve catalyst of-SCR denitrating flue gas the preparation method is as follows:
One kind being used for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, in preparation method, scandium and ZSM-
The mass percent of 5 molecular sieves is 13%, and the molar ratio of neodymium and scandium is 0.2, remaining is same as Example 2.
Comparative example 2
What this comparative example provided is used for NH3The molecular sieve catalyst of-SCR denitrating flue gas the preparation method is as follows:
One kind being used for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, in preparation method, scandium and ZSM-
The mass percent of 5 molecular sieves is 28%, and the molar ratio of neodymium and scandium is 0.7, remaining is same as Example 2.
Comparative example 3
What this comparative example provided is used for NH3The molecular sieve catalyst of-SCR denitrating flue gas the preparation method is as follows:
One kind being used for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, preparation method and embodiment 2
Difference is, without step (3), i.e., without adding soluble neodymium salting liquid, remaining is same as Example 2.
Compliance test result
(1) catalyst that the present invention synthesizes is to NOxSCR catalytic test
The molecular sieve catalyst that embodiment 1-3 and comparative example 1-3 are prepared is as subjects, respectively more than detection
6 test specimens are to NOxSCR catalytic, active testing, the condition of test are carried out on catalyst activity evaluating apparatus
Are as follows: 150-600 DEG C of temperature, reaction gas is the motor-vehicle tail-gas of simulation, wherein NO and NH3For 500ppm, 10%O2, 10%H2O,
N2For balanced gas, reaction velocity 50000h-1, it the results are shown in Table 1:
The NO of catalyst at different temperatures made from 1 embodiment and comparative example of tablexConversion ratio (%)
| Test group | 150℃ | 200℃ | 300℃ | 350℃ | 400℃ | 450℃ | 500℃ | 550℃ | 600℃ |
| Test group 1 | 85 | 89 | 91 | 93 | 94 | 92 | 90 | 89 | 82 |
| Test group 2 | 86 | 89 | 93 | 94 | 93 | 93 | 91 | 88 | 81 |
| Test group 3 | 83 | 86 | 89 | 92 | 93 | 91 | 89 | 86 | 79 |
| Test group 4 | 40 | 68 | 79 | 85 | 84 | 81 | 80 | 69 | 60 |
| Test group 5 | 39 | 67 | 78 | 83 | 84 | 82 | 78 | 67 | 61 |
| Test group 6 | 41 | 64 | 80 | 81 | 78 | 79 | 77 | 65 | 60 |
In the above table 1, test group 1-3 is corresponding in turn to molecular sieve catalyst made of embodiment 1-3, and test group 4-6 is successively
Molecular sieve catalyst made of corresponding comparative example 1-3, wherein embodiment 1-3 is the embodiment of the present invention, and table data are found out, is compared
Since the ratio of scandium, neodymium and ZSM-5 molecular sieve is not in volume proportional region of the invention in example 1-2, the conversion ratio of NOx is obviously not
The molecular sieve catalyst as made of the present invention, active temperature windows also relative narrower, illustrates between scandium, neodymium and ZSM-5 molecular sieve
When reaching certain ratio, has the function of synergy, to effectively improve catalytic activity；In addition, check experiment 6 and test
The data explanation of group 2, the addition of neodymium also have the function of widening active temperature windows.
(2) anti-SO2 poisoning performance test
The molecular sieve catalyst that embodiment 1-3 and comparative example 1-3 are prepared is as subjects, respectively more than detection
The anti-SO2 poisoning performance of 6 test specimens, method are as follows: using simulated flue gas condition by embodiment 1-3 and with comparative example 1-3 system
Standby obtained molecular sieve catalyst, which is placed in quartz ampoule fixed bed reactors, carries out activity rating, with NH3For reducing agent, typical cigarette
Under gas operating condition: NO and O2Volume fraction be respectively 0.1% and for 5%, ammonia nitrogen ratio is 1:1, SO2Volume fraction be 0.01%,
Ar is Balance Air, air speed 40000h-1.Gas analysis uses U.S. Thermo Fisher 42i-HL type NO-NO2-NOxFlue gas
Analyzer.As a result such as table 2:
The conversion ratio (%) for the NOx that catalyst made from 2 embodiment and comparative example of table changes over time
| Test group | 20min | 40min | 60min | 80min | 100min | 120min | 140min | 160min | 180min | 200min |
| Group 1 | 94.1 | 89.8 | 88.2 | 87.9 | 85.1 | 82.2 | 81.3 | 78.9 | 76.8 | 75.1 |
| Group 2 | 94.8 | 91.2 | 89.3 | 88.4 | 85.9 | 83.1 | 82.2 | 80.4 | 77.4 | 75.8 |
| Group 3 | 93.6 | 89.3 | 88.4 | 87.6 | 85.7 | 83.4 | 81.8 | 79.3 | 76.1 | 74.3 |
| Group 4 | 89.7 | 84.1 | 83.2 | 82.2 | 80.6 | 79.1 | 76.2 | 74.5 | 71.6 | 69.8 |
| Group 5 | 89.3 | 84.7 | 82.9 | 81.7 | 80.5 | 78.8 | 76.5 | 74.8 | 71.6 | 69.8 |
| Group 6 | 88.6 | 81.3 | 78.4 | 74.1 | 69.5 | 64.1 | 57.7 | 54.8 | 50.1 | 44.3 |
In the above table 1, in the above table 1, test group 1-3 is corresponding in turn to molecular sieve catalyst made of embodiment 1-3, test
Group 4-6 is corresponding in turn to molecular sieve catalyst made of comparative example 1-3, wherein embodiment 1-3 is the embodiment of the present invention, by table 2
As a result as can be seen that catalyst obtained by embodiment 1-3 is containing SO2Still there is preferable low temperature after reacting 3h in atmosphere
NH3- SCR performance, NOxConversion ratio is 75% or more.And comparative example 1-2 due in due to the ratio of scandium, neodymium and ZSM-5 molecular sieve
Not in volume proportional region of the invention, obtained catalyst is containing SO2In atmosphere after the identical time, NOxConversion ratio
Lower than embodiment 1-3, but do not add 3 high conversion rate of comparative example of neodymium relatively, illustrate the addition of neodymium and with scandium, ZSM-5 molecular sieve
The anti-SO of molecular sieve catalyst can be improved after rational proportion2Poisoning performance.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. one kind is used for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, which is characterized in that with ZSM-5 molecular sieve
Scandium, neodymium metallic element are supported on by ZSM-5 molecule by infusion process using scandium, neodymium metallic element as active component as carrier
On sieve, wherein the quality of scandium is the 16-24% of ZSM-5 molecular sieve, and the molar ratio of neodymium and scandium is 0.3-0.5；It specifically includes following
Step:
(1) ratio for being 0.3-0.5 in 16-24% and the molar ratio of neodymium and scandium that the quality of scandium is ZSM-5 molecular sieve, claims respectively
Take soluble scandium salts, soluble neodymium salt and ZSM-5 molecular sieve；Soluble scandium salts, soluble neodymium salt are separately added into two parts of volumes
It in identical ethanol solution, and is sufficiently stirred, respectively obtains soluble scandium salts solution and soluble neodymium salting liquid；
(2) ZSM-5 molecular sieve is placed in baking oven after carrying out drying and processing and is taken out, be then cooled to room temperature addition step to it
(1) in the soluble scandium salts solution obtained, and dispersing agent is added, system A is obtained after stirring, system A is placed in ultrasonic reactor
In be ultrasonically treated, obtain system B；
(3) the soluble neodymium salting liquid that step (1) obtains is added in the system B that step (2) obtain, is then stirred at room temperature
50-70min obtains system C；
(4) the system C for obtaining step (3), which is dried, obtains powder, powder is then roasted 4-5h, then naturally cool to room
It obtains after temperature for NH3The molecular sieve catalyst of-SCR denitrating flue gas.
2. according to claim 1 a kind of for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, it is special
Sign is: solubility scandium salts described in step (1) is selected from one or both of acetic acid scandium or scandium nitrate and is mixed with arbitrary proportion
Mixture.
3. according to claim 1 a kind of for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, it is special
Sign is: solubility neodymium salt described in step (1) is selected from one or both of neodymium nitrate and acetic acid neodymium and is mixed with arbitrary proportion
Mixture.
4. according to claim 1 a kind of for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, it is special
Sign is: the temperature of drying described in step (2) is 80-90 DEG C, and the time of drying and processing is 3.5-4.5h.
5. according to claim 1 a kind of for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, it is special
Sign is: dispersing agent described in step (2) is polyvinylpyrrolidone, the polyvinylpyrrolidone and soluble scandium salts solution
Volume ratio be 1-2:6-8.
6. according to claim 1 a kind of for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, it is special
Sign is: the time of step (2) described stirring is 25-65min.
7. according to claim 1 a kind of for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, it is special
Sign is: the time of step (2) described ultrasonic treatment is 50-80min；The frequency of ultrasound is 30-40kHz.
8. according to claim 1 a kind of for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, it is special
Sign is: the temperature condition of drying process described in step (4) is 100-120 DEG C, drying time 11-13h.
9. according to claim 1 a kind of for NH3The preparation method of the molecular sieve catalyst of-SCR denitrating flue gas, it is special
Sign is: the temperature of roasting described in step (4) is 400-650 DEG C.
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