CN1194814C - Method for preparing Ga*O*-Al*O* catalyst for reduction of nitrogen oxide - Google Patents
Method for preparing Ga*O*-Al*O* catalyst for reduction of nitrogen oxide Download PDFInfo
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- CN1194814C CN1194814C CNB021241414A CN02124141A CN1194814C CN 1194814 C CN1194814 C CN 1194814C CN B021241414 A CNB021241414 A CN B021241414A CN 02124141 A CN02124141 A CN 02124141A CN 1194814 C CN1194814 C CN 1194814C
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 45
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229940044658 gallium nitrate Drugs 0.000 claims abstract description 17
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 12
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001195 gallium oxide Inorganic materials 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000007794 irritation Effects 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 12
- 239000011259 mixed solution Substances 0.000 abstract description 5
- 230000001603 reducing effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 3
- 229910052593 corundum Inorganic materials 0.000 abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 3
- 239000004480 active ingredient Substances 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 229910052733 gallium Inorganic materials 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000008246 gaseous mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention relates to a method for preparing a Ca2O3-Al2O3 catalyst for reducing nitrogen oxides, which belongs to the technical field of controlling nitrogen oxide in environmental protection. The method is characterized in that gallium oxide is used as a raw material to prepare gallium nitrate, colloidal sol-gel is used for preparing boehmite, the mixed solution of gallium nitrate and ethylene glycol is added to the boehmite, and then the mixture is distillated in the mode of pressure reduction, dried and fired to prepare the Ca2O3-Al2O3 catalyst. Compared with the traditional method for preparing catalysts, the method has the advantages that the dispersion degree of the active ingredients of the catalyst is increased, the specific surface area of the catalyst is guaranteed, the optimum load of the active ingredients Ca2O3 of the catalyst is reduced by more than 3%, and the reduction rate of nitrogen oxides reaches 70% to 85% by oxidizing the catalyst in a wide interval at a low temperature when C6H4 and C8H18 containing high carbon and hydrogen content are adopted as reducing agents at high air speed. Because cheap gallium is used as the raw material to prepare the Ca2O3-Al2O3 catalyst, the cost is reduced greatly.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for reduction of oxides of nitrogen, especially relate to a kind of preparation method who makes the nitrogen oxide efficient catalytic reducing catalyst that is produced under the lean burn condition, belong to the catalyst for reduction of oxides of nitrogen preparing technical field.
Background technology
Along with expanding economy and quickening of urbanization process, automobile has become the primary pollution sources of domestic and international urban atmospheric pollution.The aggravation of energy crisis and greenhouse effects, feasible economy and the minimizing carbon dioxide (CO that how to improve fuel
2) the isothermal chamber gas purging becomes the focus of global common concern, the use of lean-burn gasoline motor car and diesel vehicle is to improve fuel economy and reduce CO
2A kind of important means of isothermal chamber gas.Although lean-burn gasoline motor car and diesel vehicle can energy-conservation about 15%, but the generation of its nitrogen oxide is inevitable, and the elevated oxygen level in its tail gas makes the activity of business-like three-way catalyst reducing NOx be subjected to serious inhibition, thereby causes the discharging of NOx in the middle of the motor-vehicle tail-gas not reach the discharge standard of increasingly stringent.Therefore, how controller motor-car nitrogen oxide is particularly controlled the focus that lean-burn gasoline motor car and diesel vehicle nitrogen oxide become domestic and international research day by day.
In recent years, the researchers of industrial circle and academia are carrying out various tests and trial both at home and abroad, nearly all non radioactive element is all by in the presence of active component or carrier, be used to prepare in the middle of the test of such catalyst, and also with between these elements or the combination between its compound also carried out many trials as the activity of such catalysts component.Up to the present, also do not research and develop out the catalyst that can be useful for the control of lean burn motor vehicle nitrogen oxide both at home and abroad.
Fritz (at Applied Catalysis B:Environmental 13 (1997) P1-25) reports that these catalyst roughly can be divided into noble metal, zeolite and metal oxide three classes.Three types catalyst is compared, and metal oxide catalyst has actual application prospect most.And for metal oxide catalyst, Hamada (at Catal Today 22 (1994) P21) has compared various types of metal oxide catalysts, finds Al
2O
3Be to have active a kind of metal oxide catalyst most, its catalytic activity and low temperature active can be by other elements of interpolation or compounds, or strengthened or solve by adding other elements or compound and making up with reducing agent.
Ken-ichi Shimizu (in Chem.Commun. (1996): under the condition of report lean burn, be reducing agent 1827-1828) with methane, Ga
2O
3-Al
2O
3Catalyst also has active preferably.Since nineteen ninety-eight, external (mainly being Japan) is to CH
4And C
3H
6Be Ga under the reducing agent lean burn condition
2O
3-Al
2O
3Selective reduction NOx has carried out certain research, and (air speed is at 10000h but mainly concentrate on low-speed
-1About) and high capacity amount (Ga
2O
3Load capacity greater than 30%) condition under carry out.
Up to the present, this method of no use prepares Ga both at home and abroad
2O
3-Al
2O
3Catalyst, and on this catalyst, carry out the research paper of high-carbon hydrogen compound selective reduction NOx and the report of patent documentation.
Summary of the invention
It is simple, low-cost and can efficient catalytic reduction Ga be arranged to nitrogen oxide to the purpose of this invention is to provide a kind of preparation technology
2O
3-Al
2O
3The Preparation of catalysts method.
In order to reduce the Preparation of catalysts cost, and prepare high performance catalyst, the inventor has carried out many research to Preparation of catalysts, comprises that mainly gallium nitrate preparation technology's exploration, improvement and other gallium salt (as gallium sulfate and gallium chloride etc.) of sol-gel catalyst preparation process are used to prepare Ga as the gallium nitrate substitute
2O
3-Al
2O
3Catalyst.Simultaneously also to high hydrocarbon C on this catalyst
6H
14, C
7H
16And C
8H
18The activity of Selective Catalytic Reduction of NO x is tentatively inquired into.And find following true: when being reducing agent, with the Ga of conventional method preparation with the propylene
2O
3-Al
2O
3Catalyst is compared, and the catalyst of this method preparation wants high to the nitrogen oxide reducing activity; When with C
6H
14, C
7H
16And C
8H
18During for reducing agent, catalyst has good activity in the low-temperature range of high-speed and broad.
The invention is characterized in: it may further comprise the steps successively:
(1) be the feedstock production gallium nitrate with the gallium oxide: gallic oxide is dissolved in salpeter solution, the mol ratio of control gallic oxide and nitric acid is 1: 6-18, during this time, add the water heating, constantly evaporating liquid after concentrating, adds water again, this operation is 6-15 hour repeatedly, till the solution that forms transparent no obvious irritation smell;
(2) treat to add ethylene glycol therein after the solution cooling in (1), the mol ratio of control aluminium isopropoxide and ethylene glycol is 1: 1-4.5;
(3) preparation boehmite vitreosol: stir and temperature 80-95 ℃ condition under, the hydrolysis aluminium isopropoxide, the mol ratio of control water and aluminium isopropoxide is 85-115: 1, drip rare nitric acid and make it to form vitreosol, wherein, the mol ratio of control nitric acid and aluminium isopropoxide is 0.1-0.3: 1, make it to form vitreosol, then, dropwise add gallium nitrate and ethylene glycol mixtures, and at room temperature stirred 12-24 hour by step (2) gained;
(4) colloidal sol with step (3) preparation places evaporation in decompression distillation 4-10 hour under the condition of water bath heating, removes colloidal sol central most of water and organic matter, during, control water temperature between 40-80 ℃, and be decompressed to 0.05 * 10
5-0.5 * 10
5Pa;
(5) residue that decompression distillation in the step (4) is obtained is at 110-150 ℃ of dry 12-24 hour, and in 500-800 ℃ of air atmosphere roasting 5-8 hour, promptly get Ga
2O
3-Al
2O
3Catalyst.
(6) catalyst that (5) step was obtained is reprinted in fixed bed reactors, the height of control beds is between 1.0-2.0cm, feed pending waste gas and reducing gas, the mol ratio of control reducing agent carbon atom and nitrogen oxide nitrogen-atoms is 3-6: 1, and the control air speed is at 50000-100000h
-1, can realize the efficient reduction of nitrogen oxide.
Use this catalyst of proof to accomplish the end in view.
Description of drawings
Fig. 1. the principle schematic of vacuum distillation apparatus.
The specific embodiment
Embodiment 1
A. the preparation of gallium nitrate: get in the middle of the red fuming nitric acid (RFNA) that 0.01 mole of gallium oxide joins 0.09 mole, stir and on heating jacket, place a few minutes, add then that deionized water begins heating evaporation, concentrates, adds water again, this process repeatedly of concentrating again 15 hours, till solution does not have the obvious irritation smell
B. treat that the solution cooling adds 0.20 mole ethylene glycol afterwards in the middle of solution;
C. prepare boehmite: it is in the middle of 92 ℃ the deionized water that the 20.423g aluminium isopropoxide is joined the 160ml temperature, stir hydrolysis after 1 hour, drip rare nitric acid 18ml (mol ratio of nitric acid and aluminium isopropoxide is 0.3: 1) aqueous solution, made it to form vitreosol in 1 hour 92 ℃ of following strong agitation again
D. then, the gallium nitrate of b gained and ethylene glycol mixed solution are dropwise joined in the middle of the boehmite colloidal sol, then, stirred at ambient temperature 24 hours,
E. after, resulting colloidal sol is placed in 55 ℃ the water-bath and 0.05 * 10
5Under the vacuum degree condition of Pa, the organic solvent in the middle of the reduction vaporization colloidal sol 6 hours,
F. next, last 110 ℃ baking oven inner dryings 24 hours, roasting is 8 hours under air atmosphere and 500 ℃ of conditions, promptly obtains Ga
2O
3-Al
2O
3Catalyst.
This catalyst when being reducing agent with the heptane, with the nitric oxide of 1000ppm, the heptane of 450ppm, 10% oxygen, remaining reaction gaseous mixture are helium, the useful load of catalyst is 250mg.When air speed is 50000h
-1, in 350-400 ℃ temperature range, the efficient of catalyst reduction nitrogen oxide can reach 65-85%.
Embodiment 2
A. the preparation of gallium nitrate: get in the middle of the red fuming nitric acid (RFNA) that 0.01 mole of gallium oxide joins 0.12 mole, stir and on heating jacket, place a few minutes, add then that deionized water begins heating evaporation, concentrates, adds water again, this process repeatedly of concentrating again 12 hours, till solution does not have the obvious irritation smell
B. treat that the solution cooling adds 0.26 mole ethylene glycol afterwards in the middle of solution;
C. prepare boehmite: it is in the middle of 90 ℃ the deionized water that the 20.423g aluminium isopropoxide is joined the 170ml temperature, stir hydrolysis after 1 hour, drip rare nitric acid 18ml (mol ratio of nitric acid and aluminium isopropoxide is 0.25: 1) aqueous solution, made it to form vitreosol in 1 hour 90 ℃ of following strong agitation again
D. then, the gallium nitrate for preparing among a and ethylene glycol mixed solution are dropwise joined in the middle of the boehmite colloidal sol, then, stirred at ambient temperature 12 hours,
E. after, resulting colloidal sol is placed in 64 ℃ the water-bath and 0.1 * 10
5Under the vacuum degree condition of Pa, the organic solvent in the middle of the reduction vaporization colloidal sol 7 hours, next last 120 ℃ baking oven inner dryings 20 hours, roasting is 6 hours under air atmosphere and 600 ℃ of conditions, promptly obtains Ga
2O
3-Al
2O
3Catalyst.
When f. being reducing agent with the octane, with the nitric oxide of 1000ppm, the octane of 375ppm, 10% oxygen, remaining reaction gaseous mixture are nitrogen (N
2), the useful load of catalyst is 250mg, air speed is 60000h
-1, can reach 70-88% in the efficient of 375-475 ℃ temperature range catalyst reduction nitrogen oxide.
Embodiment 3
A. the preparation of gallium nitrate: get in the middle of the red fuming nitric acid (RFNA) that 0.01 mole of gallium oxide joins 0.15 mole, stir and on heating jacket, place a few minutes, add then that deionized water begins heating evaporation, concentrates, adds water again, this process repeatedly of concentrating again 10 hours, till solution does not have the obvious irritation smell
B. treat that the solution cooling adds 0.28 mole ethylene glycol afterwards in the middle of solution;
C. prepare boehmite: it is in the middle of 88 ℃ the deionized water that the 20.423g aluminium isopropoxide is joined the 175ml temperature, stir hydrolysis after 1 hour, drip rare nitric acid 18ml (mol ratio of nitric acid and aluminium isopropoxide is 0.20: 1) aqueous solution, made it to form vitreosol in 1 hour 90 ℃ of following strong agitation again
D. then, gallium nitrate and the ethylene glycol mixed solution for preparing in (1) dropwise joined in the middle of the boehmite colloidal sol, then, stirred at ambient temperature 16 hours,
E. after, resulting colloidal sol is placed in 75 ℃ the water-bath and 0.15 * 10
5Under the vacuum degree condition of Pa, the organic solvent in the middle of the reduction vaporization colloidal sol 8 hours,
F. next, last 130 ℃ bellows inner dryings 16 hours, roasting is 5.5 hours under air atmosphere and 650 ℃ of conditions, promptly obtains Ga
2O
3-Al
2O
3Catalyst.
When being reducing agent with the hexane, with the nitric oxide of 1000ppm, the hexane of 500ppm, 10% oxygen, remaining reaction gaseous mixture are nitrogen, and the useful load of catalyst is 250mg, and air speed is 60000h
-1, can reach 72-95% in the efficient of 375-475 ℃ temperature range catalyst reduction nitrogen oxide.
Embodiment 4 (reference)
A. the preparation of gallium nitrate: get in the middle of the red fuming nitric acid (RFNA) that 0.01 mole of gallium oxide joins 0.18 mole, stir and on heating jacket, place a few minutes, add then that deionized water begins heating evaporation, concentrates, adds water again, this process repeatedly of concentrating again 8 hours, till solution does not have the obvious irritation smell
B. treat that the solution cooling adds 0.28 mole ethylene glycol afterwards in the middle of solution;
C. prepare boehmite: it is in the middle of 85 ℃ the deionized water that the 20.423g aluminium isopropoxide is joined the 180ml temperature, stir hydrolysis after 1 hour, drip rare nitric acid 18ml (mol ratio of nitric acid and aluminium isopropoxide is 0.12: 1) aqueous solution, made it to form vitreosol in 1 hour 90 ℃ of following strong agitation again
D. then, gallium nitrate and the ethylene glycol mixed solution for preparing in (1) dropwise joined in the middle of the boehmite colloidal sol, then, stirred at ambient temperature 12 hours,
E. after, resulting colloidal sol is placed in 80 ℃ the water-bath and 0.2 * 10
5Under the vacuum degree condition of Pa, the organic solvent in the middle of the reduction vaporization colloidal sol 10 hours,
F. next, last 140 ℃ bellows inner dryings 12 hours, roasting is 5 hours under air atmosphere and 800 ℃ of conditions, promptly obtains Ga
2O
3-Al
2O
3Catalyst.
When thinking the propylene reducing agent, with the nitric oxide of 1000ppm, the propylene of 1000ppm, 10% oxygen, remaining reaction gaseous mixture are helium, the useful load of catalyst is 250mg.When air speed is 30000h
-1, can reach 60-97% in the efficient of 425-500 ℃ temperature range catalyst reduction nitrogen oxide.
Decompression distillation principle and device that the present invention uses are seen Fig. 1.The 1st, thermometer, the 2nd, delivery port, the 3rd, condenser pipe, the 4th, water inlet, the 5th, water-bath, the 6th, recirculated water vavuum pump, the 7th, pressure modulating opening.
The catalyst of method of the present invention preparation is compared with the catalyst of conventional method preparation, and adopting the gallium oxide of cheapness on the one hand is raw material, make the Preparation of catalysts cost reduce greatly (be about with the import gallium nitrate prepare the catalyst cost 1/80th); On the other hand in the Preparation of catalysts process, the method that traditional sol-gel is prepared catalyst is improved, with moisture and the organic matter in the middle of the alternative traditional heating backflow of the decompression distillation removal colloidal sol, both guaranteed the specific area of catalyst, improved the decentralization of catalyst activity component again, this makes catalyst activity component Ga
2O
3Optimum load amount reduce more than 3%.Find simultaneously at air speed 50000h
-1Condition under, with the hydrocarbon (C of height
6H
14, C
7H
16And C
8H
18) when being reducing agent, this catalyst is (350-450 ℃) in the low-temperature range of broad, and the reduction of nitrogen oxide is had 70-85% efficient.
Claims (1)
1, nitrogen oxide reduction Ga
2O
3-Al
2O
3The Preparation of catalysts method contains sol-gel and prepares Al
2O
3The step of catalyst or carrier is characterized in that: it may further comprise the steps successively:
(1) be the feedstock production gallium nitrate with the gallium oxide: gallic oxide is dissolved in salpeter solution, the mol ratio of control gallic oxide and nitric acid is 1: 6-18, during this time, add the water heating, constantly evaporating liquid after concentrating, adds water again, this operation is 6-15 hour repeatedly, till the solution that forms transparent no obvious irritation smell;
(2) treat to add ethylene glycol therein after the solution cooling in (1), the mol ratio of control aluminium isopropoxide and ethylene glycol is 1: 1-4.5;
(3) preparation boehmite vitreosol: stir and temperature 80-95 ℃ condition under, the hydrolysis aluminium isopropoxide, the mol ratio of control water and aluminium isopropoxide is 85-115: 1, drip rare nitric acid and make it to form vitreosol, wherein, the mol ratio of control nitric acid and aluminium isopropoxide is 0.1-0.3: 1, make it to form vitreosol, then, dropwise add gallium nitrate and ethylene glycol mixtures, and at room temperature stirred 12-24 hour by step (2) gained;
(4) colloidal sol with step (3) preparation placed the water-bath heating decompression distillation 4-10 hour down, most of water and organic matter in the middle of the evaporative removal colloidal sol, during, control water temperature between 40-80 ℃, and be decompressed to 0.5 * 10
5-0.05 * 10
5Pa;
(5) residue that decompression distillation in the step (4) is obtained is at 110-150 ℃ of dry 12-24 hour, and in 500-800 ℃ of air atmosphere roasting 5-8 hour, promptly get Ga
2O
3-Al
2O
3Catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021241414A CN1194814C (en) | 2002-07-12 | 2002-07-12 | Method for preparing Ga*O*-Al*O* catalyst for reduction of nitrogen oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021241414A CN1194814C (en) | 2002-07-12 | 2002-07-12 | Method for preparing Ga*O*-Al*O* catalyst for reduction of nitrogen oxide |
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| Publication Number | Publication Date |
|---|---|
| CN1467025A CN1467025A (en) | 2004-01-14 |
| CN1194814C true CN1194814C (en) | 2005-03-30 |
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| CN102921178A (en) * | 2012-11-19 | 2013-02-13 | 青岛大学 | Anti-oxidization evaporation and drying device and method |
| BR112016012791B1 (en) * | 2013-12-16 | 2021-06-08 | Dow Global Technologies Llc | heterogeneous catalyst for dehydrogenation of alkanes and catalyst |
| CN107970928B (en) * | 2016-10-24 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of preparing furan through decarbonylation of furfural catalyst, preparation method and application |
| CN111482179B (en) * | 2020-04-23 | 2021-08-17 | 西南化工研究设计院有限公司 | Low-temperature Cu-series conversion catalyst and preparation method and application thereof |
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