CN114247473A - For decomposing N2Metal-formed catalyst of O and preparation method thereof - Google Patents
For decomposing N2Metal-formed catalyst of O and preparation method thereof Download PDFInfo
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- CN114247473A CN114247473A CN202111502612.7A CN202111502612A CN114247473A CN 114247473 A CN114247473 A CN 114247473A CN 202111502612 A CN202111502612 A CN 202111502612A CN 114247473 A CN114247473 A CN 114247473A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 70
- 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 70
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 23
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 20
- 238000004898 kneading Methods 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000010298 pulverizing process Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 235000011837 pasties Nutrition 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000011812 mixed powder Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000005470 impregnation Methods 0.000 description 16
- 239000010949 copper Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000007580 dry-mixing Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- -1 iron ion Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 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 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Abstract
The invention provides a method for decomposing N2The metal forming catalyst of O is prepared by the steps of high-temperature calcination pretreatment of a molecular sieve carrier, kneading and forming with an auxiliary agent and the like, and then is subjected to metal modification to obtain the forming catalyst with high catalytic activity, high mechanical strength and high-temperature stability. The metal forming catalyst can meet the requirement of N2The high-efficiency decomposition of O can not affect NO and NO2The yield of the method plays a positive role in emission reduction of waste gas in the nitric acid industry.
Description
Technical Field
The invention relates to the technical field of nitric acid production by an ammonia contact oxidation method, in particular to a method for decomposing N2O metal forming catalyst and a preparation method thereof.
Background
Nitric acid is an important chemical raw material and has important application in many fields. N is generated in the current mainstream process for producing nitric acid by ammonia contact oxidation method2O and NOxTwo pollutants which can cause various atmospheric problems such as greenhouse effect, ozone layer damage, haze and photochemical smog have great threat and harm to the living environment of human beings, so that the nation gradually controls N in recent years2The problem of O emission. The process for producing nitric acid by ammonia contact oxidation method isUnder the high temperature condition of 800 ℃ and 900 ℃, metal platinum is used as a catalyst, NH3And O2The reaction produces a large amount of NO, which is further oxidized to produce NO2，NO2Finally reacting with H in an absorption tower2And reacting O to generate nitric acid. In the process, a byproduct greenhouse gas N is generated at the platinum net2O，N2O can not be absorbed by the aqueous solution and is finally directly discharged into the atmosphere, the O stays in the nature for 70-100 years, and the greenhouse effect of the O is CO2310 times of the total weight of the carbon dioxide, which is listed as a non-CO by the United nations2Greenhouse gases.
Patent CN101795765A elaborates emission reduction N in industrial production process of nitric acid2Three measures of O, namely: (1) selective oxidation of ammonia to NO and avoidance of undesirable N by changing the chemical composition of the oxidation catalyst2O is formed; (2) direct reduction of emission N2O catalyst is filled below a noble metal net for ammoxidation reaction, but the N is reduced2The working temperature of the O catalyst is relatively higher, and is generally at 800-1000 ℃; (3) n contained in the off-gas leaving the absorption column2Catalytic decomposition of O, general reduction of N2The working temperature of the O catalyst is 200-700 ℃.
In view of the above solution, an economical solution is to charge a suitable specific catalyst under a noble metal platinum mesh, in N2When the O leaves the noble metal net, the O is directly treated in a nitric acid oxidation furnace, thereby avoiding additional energy consumption caused by adding additional devices. But this scheme is for decomposition of N2The requirements for O catalysts are extremely high due to the extreme conditions to which they are adapted: about 40000h-1The space velocity of (A), the reaction temperature of 850 ℃, the water content of 17% and the NO content of 10% in the gas, only put high demands on the activity and selectivity of the catalyst, and on the mechanical strength and thermal stability thereof. In addition, Pt combustion products on the noble metal mesh also precipitate on the catalyst and decompose the desired oxidation product NO, resulting in a large drop in nitric acid yield.
Therefore, a method for directly controlling N in the nitric acid production process is developed2O is purified and decomposed to satisfy the requirement on N2High-efficiency decomposition of O without influence on NO and NO2The yield of the catalystTherefore, the problem to be solved is needed.
Disclosure of Invention
In order to solve the problems, the invention provides a method for decomposing N in a nitric acid oxidation furnace2The metal forming catalyst of O is prepared by the steps of carrying out high-temperature calcination pretreatment on a molecular sieve carrier, kneading and forming with an auxiliary agent and the like, and then carrying out metal modification on the molecular sieve carrier to obtain the forming catalyst with high catalytic activity, high mechanical strength and high temperature stability. The metal forming catalyst can meet the requirement of N2The high-efficiency decomposition of O is realized without influencing NO and NO2The yield of the method plays a positive role in emission reduction of waste gas in the nitric acid industry.
The technical scheme of the invention is as follows:
the invention provides a method for decomposing N2The metal forming catalyst of O comprises the following raw materials in parts by weight:
molecular sieve carrier: 70-100 parts by weight;
metal monoatomic: loading 1.0-5.0% of loading capacity on the molecular sieve carrier;
adhesive: 20-40 parts by weight;
extrusion aid: 2-5 parts by weight;
peptizing agent: 8-15 parts by weight;
wherein the molecular sieve carrier is selected from one or more than two of RUB-50, SSZ-16 and SSZ-39;
the metal single atom is selected from one or more than two of Cu, Fe, Zn, Mg, Ni and Mn;
the water-powder ratio of the metal forming catalyst is 60-70 mL/g.
Further, the metal single atom is a combination of Cu and Fe, a combination of Fe, Ni and Mg, or a combination of Cu, Zn and Mn. More preferably a combination of Cu, Zn and Mn.
Further, the loading amount of the metal atoms is 1.0-5.0% based on the mass of the molecular sieve carrier.
Furthermore, the particle size of the molecular sieve carrier is 100-150 meshes.
Further, the silica to alumina ratio of the molecular sieve support is 25 to 40, preferably 30 to 35, and more preferably 30.
Further, the binder is one or more than two of pseudo-boehmite powder, acidic silica sol, aluminum oxide and the like.
Furthermore, the extrusion aid is one or more than two of sesbania powder, polycarboxylic acid glycerol and the like. Preferably, the extrusion aid is sesbania powder.
Further, the peptizing agent is one or more than two of nitric acid, acetic acid, citric acid and the like, and the solution mass solubility of the peptizing agent is 60-68 wt%. The peptizing agent is preferably 68 wt% nitric acid.
Furthermore, the compressive strength of the metal forming catalyst is 90-150N/cm.
Furthermore, in the final catalyst product of the invention, the extrusion assistant, the peptizing agent and the water in the raw materials are completely volatilized after being dried and calcined at high temperature,
the invention also provides a preparation method of the metal forming catalyst, which comprises the following steps:
and step S1: preparation of molded molecular sieve support
S1-1: high-temperature calcination:
calcining the molecular sieve carrier, heating to 540-550 ℃ at a heating rate of 2-5 ℃/min, calcining at a constant temperature for 6-10h after reaching a final temperature, and then cooling to room temperature;
s1-2: pulverization:
pulverizing and sieving the calcined molecular sieve carrier;
s1-3: dry blending, kneading and extrusion molding:
mixing the molecular sieve carrier obtained in the step S1-2 with a binder, an extrusion aid, a peptizing agent and water according to the weight part ratio of the raw materials, and extruding, aging and extruding the obtained muddy material to obtain a Raschig ring structured molded molecular sieve carrier;
s1-4: drying and calcining the formed molecular sieve carrier;
and step S2: dipping modification:
measuring certain deionized water according to the saturated water absorption capacity of the formed molecular sieve carrier, calculating the mass of required metal salt, dissolving the metal salt into the deionized water, dropwise adding the metal salt solution into the formed molecular sieve carrier, continuously stirring in the dropwise adding process to ensure that the metal salt solution is uniformly absorbed by the formed molecular sieve carrier, drying the metal salt solution in a drying box at 100-120 ℃ for 8-10 hours after water bath at constant temperature of 40-60 ℃ for 6-8 hours, and calcining the metal salt solution in a muffle furnace at 550 ℃ for 6-10 hours to obtain the final metal formed catalyst.
Further, in step S1-1, the purpose of subjecting the molecular sieve support to high-temperature calcination pretreatment before use is to remove volatile components in the molecular sieve by pyrolysis, so that the finally formed catalyst maintains stable catalytic performance and the mechanical strength of the catalyst can be improved.
Further, in step S1-2, the conventional powdered or granular catalyst has the disadvantages of large pressure drop, easy reactor blockage and the like at high fluid flow rate of the reaction, and cannot be directly applied to industrial production, so the present invention performs grinding pulverization after high temperature calcination of the molecular sieve carrier, and controls the particle size within a certain range, so that the molecular sieve carrier has certain shape, particle size and industrial strength.
Further, in step S1-3, the binder and the extrusion aid are added to the molecular sieve carrier to mix, the peptizing agent is added to deionized water to prepare an acidic dilute solution, and finally the acidic olefin solution is added to the powder to be sufficiently kneaded to obtain a pasty material.
Further, in step S1-3, extruding the prepared mud-like material into a mud blank in a double-screw extruder with the extrusion rotation speed of 40-60 r/min, aging a mud blank sample in a cool and dry place for 6-8h, and then putting the aged blank into an extrusion molding machine to be molded by a grinding tool to obtain the molded molecular sieve carrier. Furthermore, the formed molecular sieve carrier is a formed molecular sieve with Raschig ring structure, the thickness of the formed molecular sieve carrier is 20 x 20mm, and the wall thickness of the formed molecular sieve carrier is 3 mm.
Further, in step S1-4, the molded molecular sieve carrier is dried in a forced air drying oven at 100-120 ℃ for 4-6 h, then calcined in a muffle furnace at 550-650 ℃ for 6-8h, and then naturally cooled to room temperature.
Further, in step S2, the metal salt is Cu2+、Fe2+、Zn2+、Mg2+、Ni2+、Mn2+One or more than two nitrate, sulfate or oxalate.
The technical scheme of the invention has the following beneficial effects:
(1) the metal forming catalyst of the invention completely decomposes N2O at high temperature, the conversion rate is 100%, and simultaneously NO reaction is caused;
(2) the metal forming catalyst has strong stability and can stably decompose N at the temperature of 800-2O。
(3) The catalyst has better mechanical strength, can effectively support the platinum net frame, and can not increase the production energy consumption.
(4) The metal modified catalyst has good plasticity and is beneficial to the successful extrusion molding of the catalyst.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
Example 1
A Fe/SSZ-16 shaped catalyst is composed of the following raw materials:
molecular sieve carrier: SSZ-16, 75 parts by weight;
metal monoatomic: 1.923 parts by weight of Fe;
adhesive: 25 parts of pseudo-boehmite powder;
extrusion aid: 3 parts of sesbania powder;
peptizing agent: 10 parts of nitric acid;
the preparation method comprises the following steps:
s1-1: high-temperature calcination:
200g of SSZ-16 molecular sieve is placed in an evaporation dish, is placed in a muffle furnace to be heated from room temperature to 540 ℃ at the heating rate of 2 ℃/min, is calcined for 6 hours at constant temperature and then is naturally cooled to the room temperature;
s1-2: pulverization:
pulverizing the SSZ-16 molecular sieve calcined at high temperature, and sieving to obtain a sieved SSZ-16 molecular sieve with the particle size of 150 meshes;
s1-3: dry blending, kneading and extrusion molding:
dry mixing: weighing 75g of SSZ-16 molecular sieve, 25g of pseudo-boehmite powder and 3g of sesbania powder, and putting the mixture into a mixer to be uniformly stirred for 20-30 minutes at the temperature of about 30 ℃;
kneading: slowly and uniformly adding 65ml of water and 10g of nitric acid (the concentration is 68 wt%) into the mixed material, stirring and kneading for 20-30 minutes, and controlling the temperature to be about 30 ℃;
and (3) extrusion molding: kneading the kneaded mud-like material into a mud blank in an F-26 double-screw extruder with the extrusion rotating speed of 50r/min, aging a mud blank sample in a cool and dry place for 6 hours, then putting the aged blank into an extrusion molding machine, and performing extrusion molding by using a grinding tool to prepare a molded catalyst with a Raschig ring structure, wherein the particle size of the molded catalyst is 20 x 20mm, and the wall thickness of the molded catalyst is 3 mm;
s1-4: drying and calcining the formed molecular sieve carrier;
and (3) placing the formed molecular sieve carrier subjected to extrusion molding into a forced air drying oven, continuously drying for 6h at 110 ℃, then heating to 550 ℃ from room temperature in a muffle furnace at the heating rate of 2 ℃/min, and naturally cooling to room temperature after calcining for 6h at constant temperature.
S2: dipping modification:
the metal iron loading was 2.5%, 13.911g of iron nitrate (Fe (NO)3)3·3H2O) is dissolved in 44g of deionized water to prepare iron ion impregnation liquid, the impregnation liquid is slowly dripped into a formed molecular sieve carrier, the mixture is continuously stirred in the dripping process to ensure that the solution is uniformly absorbed by the carrier, and then the mixture is dried in a drying oven at the constant temperature of 60 ℃, water bath of 6h and the temperature of 110 ℃ for 10h and then calcined in a muffle furnace at the temperature of 550 ℃ for 6h to prepare the finally required Fe/SSZ-16 formed catalyst with a Raschig ring structure, wherein the Fe/SSZ-16 supported catalyst is 20 x 20mm and the wall thickness of the Fe/SSZ-16 formed catalyst is 3 mm.
Example 2
A Cu/RUB-50 shaped catalyst is composed of the following raw materials:
molecular sieve carrier: RUB-50, 80 parts by weight;
metal monoatomic: 1.633 parts by weight of Cu;
adhesive: 20 parts of pseudo-boehmite powder;
extrusion aid: 2.5 parts of sesbania powder;
peptizing agent: 10 parts of nitric acid;
the preparation method comprises the following steps:
s1-1: high-temperature calcination:
putting a 200 gRBB-50 molecular sieve in an evaporation dish, heating the evaporation dish in a muffle furnace at a heating rate of 2 ℃/min from room temperature to 540 ℃, calcining the evaporation dish at a constant temperature for 6 hours, and naturally cooling the calcination dish to the room temperature;
s1-2: pulverization:
pulverizing the RUB-50 molecular sieve calcined at high temperature, and sieving to obtain a sieved RUB-50 molecular sieve with the particle size of 150 meshes;
s1-3: dry blending, kneading and extrusion molding:
dry mixing: weighing 80g of RUB-50 molecular sieve, 20g of pseudo-boehmite powder and 2.5g of sesbania powder, and putting the mixture into a mixer to be uniformly stirred for 20-30 minutes at the temperature of about 30 ℃;
kneading: slowly and uniformly adding 60ml of water and 10g of nitric acid (the concentration is 68 wt%) into the mixed material, stirring and kneading for 20-30 minutes, and controlling the temperature to be about 30 ℃;
and (3) extrusion molding: kneading the kneaded mud-like material into a mud blank in an F-26 double-screw extruder with the extrusion rotating speed of 50r/min, aging a mud blank sample in a cool and dry place for 8 hours, then putting the aged blank into an extrusion molding machine, and performing extrusion molding by using a grinding tool to prepare a molded catalyst with a Raschig ring structure, wherein the particle size of the molded catalyst is 20 x 20mm, and the wall thickness of the molded catalyst is 3 mm;
s1-4: drying and calcining the formed molecular sieve carrier;
placing the molded molecular sieve carrier subjected to extrusion molding in a forced air drying oven for continuous drying at 120 ℃ for 4h, then heating the molded molecular sieve carrier from room temperature to 550 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and naturally cooling to the room temperature after calcining at the constant temperature for 6 h;
s2: dipping modification:
the amount of metallic copper supported was 2.0%, and 6.2g of copper nitrate (Cu (NO)3)2·3H2O) is dissolved in 43g of deionized water to prepare iron ion impregnation liquid, the impregnation liquid is slowly dripped into a formed molecular sieve carrier, the mixture is continuously stirred in the dripping process to ensure that the solution is uniformly absorbed by the carrier, and then the solution is dried in a drying oven at the constant temperature of 60 ℃, a water bath of 6h and the temperature of 110 ℃ for 8h and then calcined in a muffle furnace at the temperature of 550 ℃ for 6h to prepare the finally required formed catalyst of the Raschig ring structure which is loaded with the metallic iron and has the thickness of 20 x 20mm and the wall of 3 mm.
Example 3
A shaped Fe and Cu/SSZ-39 catalyst is prepared from the following raw materials:
molecular sieve carrier: SSZ-39, 70 parts by weight;
metal monoatomic: fe and Cu, both 1.066 parts by weight;
adhesive: pseudo-boehmite powder, 30 parts by weight;
extrusion aid: 3.5 parts of sesbania powder;
peptizing agent: 13 parts by weight of nitric acid;
the preparation method comprises the following steps:
s1-1: high-temperature calcination:
200g of SSZ-39 molecular sieve is placed in an evaporation dish, is placed in a muffle furnace to be heated from room temperature to 540 ℃ at the heating rate of 2 ℃/min, is calcined for 6 hours at constant temperature and then is naturally cooled to the room temperature;
s1-2: pulverization:
pulverizing the SSZ-39 molecular sieve calcined at high temperature, and sieving to obtain a sieved SSZ-39 molecular sieve, wherein the particle size of the sieved SSZ-39 molecular sieve is controlled to be 150 meshes;
s1-3: dry blending, kneading and extrusion molding:
dry mixing: weighing 70g of SSZ-39 molecular sieve, 30g of pseudo-boehmite powder and 3.5g of sesbania powder, and putting the mixture into a mixer to be stirred uniformly for 20-30 minutes at the temperature of about 30 ℃;
kneading: slowly and uniformly adding 65ml of water and 13g of nitric acid (the concentration is 68 wt%) into the mixed material, stirring and kneading for 20-30 minutes, and controlling the temperature to be about 30 ℃;
and (3) extrusion molding: kneading the kneaded mud-like material into a mud blank in an F-26 double-screw extruder with the extrusion rotating speed of 50r/min, aging a mud blank sample in a cool and dry place for 8 hours, then putting the aged blank into an extrusion molding machine, and performing extrusion molding by using a grinding tool to prepare a molded catalyst with a Raschig ring structure, wherein the particle size of the molded catalyst is 20 x 20mm, and the wall thickness of the molded catalyst is 3 mm;
s1-4: drying and calcining the formed molecular sieve carrier;
placing the molded molecular sieve carrier subjected to extrusion molding in a forced air drying oven for continuous drying at 110 ℃ for 4h, then heating the molded molecular sieve carrier from room temperature to 550 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and naturally cooling to the room temperature after calcining at the constant temperature for 6 h;
s2: dipping modification:
the amounts of metallic copper and iron supported were 1.5% respectively, and 8g of copper nitrate (Cu (NO)3)2·3H2O)11g iron nitrate (Fe (NO)3)3·3H2O) is dissolved in 53g of deionized water to prepare iron ion impregnation liquid, the impregnation liquid is slowly dripped into a formed molecular sieve carrier, the mixture is continuously stirred in the dripping process to ensure that the solution is uniformly absorbed by the carrier, and then the mixture is dried in a drying oven at the constant temperature of 60 ℃, a water bath of 6h and the temperature of 110 ℃ for 8h and then calcined in a muffle furnace at the temperature of 550 ℃ for 6h to prepare the finally required formed catalyst of the Raschig ring structure which loads copper and iron with the metal of 20 x 20mm and the wall thickness of 3 mm.
Comparative example 1
In comparative example 1, the preparation and formulation were identical to those of example 1 except that there was no impregnation modification of step S-2 of example 1, and in comparative example 1, an unmodified Raschig ring structured shaped catalyst was finally obtained.
Comparative example 2
In comparative example 2, the preparation and formulation were identical to those of example 2 except that there was no impregnation modification of step S-2 of example 2, and in comparative example 2, an unmodified Raschig ring structured shaped catalyst was finally obtained.
Comparative example 3
In comparative example 3, the preparation and formulation were identical to those of example 3 except that there was no impregnation modification of step S-3 of example 3, and in comparative example 3, an unmodified Raschig ring structured shaped catalyst was finally obtained.
Test example
(1) The mechanical strength test method of the shaped catalyst is as follows:
the strength of the molded catalysts prepared in examples 1, 2 and 3 and comparative examples 1, 2 and 3 was measured using a DL ii smart particle strength tester, and 20 segments of the catalyst having the same size were used in each group for the compressive strength test, and finally the average value was taken in N/cm.
(2) The method for testing the plasticity of the formed catalyst comprises the following steps:
the plasticity is determined by studying the relation between stress and strain of the sample in the stress process. The smaller the plasticity number, the better the plasticity of the catalyst blank, whereas the worse the plasticity of the catalyst blank. Plasticity is an important index for whether the blank can be successfully extruded and molded, and good plasticity can improve the smoothness of the texture of the molded catalyst. All the catalyst blanks of the examples and comparative examples were each produced as F28 x 38mm cylinders, which were placed in the center of the platen of a KS-B microcomputer plasticity meter, and the cylinders were deformed as the pressure on the platen increased and the plasticity on the meter was read when the platen pressure no longer increased.
The plasticity degree calculation method comprises the following steps:
in the formula: r-the plasticity of the blank;
a — constant, this value is 1.8 for F28 x 38mm cylinder samples;
F10-the pressure value at which the sample is compressed by 10%;
F50-the value of the pressure at which the sample is compressed by 50%.
(3) The denitration activity test method of the formed catalyst comprises the following steps:
evaluation of ActivityThe device is a gas-solid phase catalytic reaction evaluation device. The molded catalyst was processed into a small test piece having a mass of 0.5g and placed in a reaction tube. Introducing carrier gas He, introducing 1000ppm of NO and 1500ppm of N after adsorption equilibrium2Mixed gas of O, O2The content is adjusted to 8.5 percent, and the reaction space velocity is set to 100000h-1. The reaction temperature is increased to 800 ℃ from room temperature, the reaction is continued for 10h, and N is respectively tested for 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h and 10h2O and NOXThe residual concentration of N is calculated according to a formula to obtain N2O、NOXAnd (4) conversion rate.
The catalytic activity of the shaped catalyst is represented by N2O conversion and NOXThe conversion rate is reflected by the following calculation formula:
mechanical Strength, N, of shaped catalysts prepared in different examples and comparative examples2O conversion, NOXThe conversion is shown in tables 1, 2 and 3.
TABLE 1 mechanical Strength of shaped catalysts prepared in different examples and comparative examples
| Examples of the invention | Mechanical Strength (N/cm) |
| Example 1 | 90.65 |
| Example 2 | 75.46 |
| Example 3 | 121.23 |
| Comparative example 1 | 60.43 |
| Comparative example 2 | 52.04 |
| Comparative example 3 | 89.80 |
From the results in table 1, it is seen that the mechanical strength of the shaped catalyst modified by metal impregnation is significantly improved. Furthermore, as seen from the comparison of the mechanical strength of examples 1 to 3, the mechanical strength of the shaped catalyst supporting two metals was significantly improved over that of the shaped catalyst supporting only one metal.
TABLE 2 plasticity of shaped catalysts prepared in different examples and comparative examples
| Examples of the invention | Degree of plasticity |
| Example 1 | 0.177 |
| Example 2 | 0.181 |
| Example 3 | 0.205 |
| Comparative example 1 | 0.453 |
| Comparative example 2 | 0.398 |
| Comparative example 3 | 0.412 |
As can be seen from the test results in table 2, the plasticity of the formed catalyst obtained by metal impregnation modification is lower than that obtained without metal impregnation modification, so that the plasticity is better, and the smoothness of the texture of the formed catalyst can be improved.
TABLE 3N of shaped catalysts prepared in different examples and comparative examples2Conversion of O
From the results in Table 3, it can be seen that the N content of the shaped catalyst modified by metal impregnation2The conversion rate of O reaches 100 percent, and N is enabled within 1 hour after the catalytic reaction begins2Completely decomposing O;
and N of the shaped catalyst not modified by metal impregnation2The O conversion did not reach 100% within the first few hours. It can be seen that the shaped catalysts of examples 1-3 have higher catalytic activity and can stably decompose N at 800-2And O, the stability is enhanced.
TABLE 4 NO of shaped catalysts prepared in different examples and comparative examplesXConversion rate
From the results in table 4, the NO conversion of the shaped catalyst modified by metal impregnation was 0%, indicating NO reaction with NO;
while the shaped catalysts which were not modified by metal impregnation reacted with NO within the first few hours, it can be seen that the shaped catalysts of examples 1-3 did not affect the yield of NO, so that N was obtained2The selectivity to O is higher.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, but any modifications or equivalent variations made according to the technical spirit of the present invention are within the scope of the present invention as claimed.
Claims (10)
1. For decomposing N2The metal forming catalyst of O is characterized by comprising the following raw materials in parts by weight:
molecular sieve carrier: 70-100 parts by weight;
metal monoatomic: loading 1.0-5.0% of loading capacity on the molecular sieve carrier;
adhesive: 20-40 parts by weight;
extrusion aid: 2-5 parts by weight;
peptizing agent: 8-15 parts by weight;
wherein the molecular sieve carrier is selected from one or more than two of RUB-50, SSZ-16 and SSZ-39;
the metal single atom is selected from one or more than two of Cu, Fe, Zn, Mg, Ni and Mn;
the water-powder ratio of the metal forming catalyst is 60-70 mL/g.
2. The shaped metal catalyst according to claim 1, wherein the metal monoatomic atom is Cu, a combination of Fe, or a combination of Fe, Ni, Mg, or a combination of Cu, Zn, Mn.
3. The metal-formed catalyst according to claim 2, wherein the metal atom is supported in an amount of 1.0 to 5.0% by mass based on the mass of the molecular sieve support.
4. The metal forming catalyst according to claim 3, wherein the binder is one or more of pseudo-boehmite powder, acidic silica sol, and alumina.
5. The metal-forming catalyst of claim 4, wherein the extrusion aid is one or more of sesbania powder and polycarboxylic acid glycerol.
6. The metal catalyst according to claim 5, wherein the peptizing agent is one or more of nitric acid, acetic acid and citric acid, and the solution mass solubility of the peptizing agent is 60-68 wt%.
7. The metal forming catalyst according to claim 6, wherein the compressive strength of the metal forming catalyst is 90 to 150N/cm.
8. A method for preparing a shaped metal catalyst according to any one of claims 1 to 7, comprising the steps of:
and step S1: preparation of molded molecular sieve support
S1-1: high-temperature calcination:
calcining the molecular sieve carrier, heating to 540-550 ℃ at a heating rate of 2-5 ℃/min, calcining at a constant temperature for 6-10h after reaching a final temperature, and then cooling to room temperature;
s1-2: pulverization:
pulverizing and sieving the calcined molecular sieve carrier;
s1-3: dry blending, kneading and extrusion molding:
mixing the molecular sieve carrier obtained in the step S1-2 with a binder, an extrusion aid, a peptizing agent and water according to the weight part ratio of the raw materials, and extruding, aging and extruding the obtained muddy material to obtain a Raschig ring structured molded molecular sieve carrier;
s1-4: drying and calcining the formed molecular sieve carrier;
and step S2: dipping modification:
measuring certain deionized water according to the saturated water absorption capacity of the formed molecular sieve carrier, calculating the mass of required metal salt, dissolving the metal salt into the deionized water, dropwise adding the metal salt solution into the formed molecular sieve carrier, continuously stirring in the dropwise adding process to ensure that the metal salt solution is uniformly absorbed by the formed molecular sieve carrier, drying the metal salt solution in a drying box at 100-120 ℃ for 8-10 hours after water bath at constant temperature of 40-60 ℃ for 6-8 hours, and calcining the metal salt solution in a muffle furnace at 550 ℃ for 6-10 hours to obtain the final metal formed catalyst.
9. The method according to claim 8, wherein in step S1-3, the binder and the extrusion aid are first added to the molecular sieve support to be mixed, the peptizing agent is then added to deionized water to prepare an acidic dilute solution, and finally the acidic olefin solution is added to the mixed powder to be sufficiently kneaded to obtain the pasty material.
10. The method of claim 9, wherein in step S2, the metal salt is Cu2+、Fe2+、Zn2+、Mg2+、Ni2+、Mn2+One or more than two nitrate, sulfate or oxalate.
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