CN114247473B - For decomposing N 2 O metal forming catalyst and preparation method thereof - Google Patents
For decomposing N 2 O metal forming catalyst and preparation method thereof Download PDFInfo
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- CN114247473B CN114247473B CN202111502612.7A CN202111502612A CN114247473B CN 114247473 B CN114247473 B CN 114247473B CN 202111502612 A CN202111502612 A CN 202111502612A CN 114247473 B CN114247473 B CN 114247473B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 82
- 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 82
- 238000000034 method Methods 0.000 claims abstract description 25
- 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 21
- 238000004898 kneading Methods 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000010298 pulverizing process Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- 239000012266 salt solution Substances 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
- 238000001816 cooling Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 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
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 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
- 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
- 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
- 235000011187 glycerol Nutrition 0.000 claims 1
- 239000011812 mixed powder Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 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 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000010949 copper Substances 0.000 description 14
- 238000005470 impregnation Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000227 grinding 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
- 230000002431 foraging effect Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- -1 iron ion Chemical class 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 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
- 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
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 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
- 239000000047 product Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct 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
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000035882 stress Effects 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 N 2 The metal forming catalyst of O is prepared through high temperature calcination pretreatment of molecular sieve carrier, kneading and forming of assistant, and metal modification to obtain the catalyst with high catalytic activity, high mechanical strength and high temperature stability. The metal forming catalyst can not only meet the requirement of N 2 O is decomposed efficiently without affecting NO and NO 2 Plays a positive role in reducing the emission 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 N 2 O metal forming catalyst and its preparation process.
Background
Nitric acid is an important chemical raw material and has important application in a plurality of fields. N is generated in the process of producing nitric acid by the mainstream ammonia contact oxidation method at present 2 O and NO x Two pollutants, which cause various atmospheric problems such as greenhouse effect, ozone layer damage, haze and photochemical smog, have great threat and harm to human living environment, so the N is gradually controlled in recent years 2 O emissions. The process for producing nitric acid by ammonia contact oxidation method is characterized by that under the condition of 800-900 deg.C, under the condition of high-temperature, metal platinum is used as catalyst, NH 3 With O 2 The reaction generates a large amount of NO, and the NO is further oxidized to generate NO 2 ，NO 2 Finally in the absorption tower with H 2 O reacts to form nitric acid. In the process, a byproduct greenhouse gas N is generated at the platinum gauze 2 O，N 2 O can not be absorbed by the aqueous solution and is finally discharged to the atmosphere directly, and stays in the natural world for 70-100 years, and the greenhouse effect is CO 2 Has been listed by the United nations as a non-CO 2 Greenhouse gases.
Patent CN101795765A details the reduction of N in the industrial production of nitric acid 2 Three measures of O, namely: (1) Selective oxidation of ammonia to NO and avoidance of undesired N by changing the chemical composition of the oxidation catalyst 2 O is formed; (2) Directly reduce the emission N 2 O catalyst is arranged below a noble metal net for ammoxidation reaction, but emission N is reduced 2 The operating temperature of the O catalyst is relatively high, oneTypically at 800-1000 ℃; (3) N contained in the offgas leaving the absorption column 2 O catalytic decomposition, generally reducing emission N 2 The operating temperature of the O catalyst is 200-700 ℃.
From the above solution, an economical solution is to load a noble metal platinum mesh with a suitable specific catalyst in N 2 O leaves the noble metal net and is directly treated in the nitric acid oxidation furnace, so that the extra energy consumption caused by adding extra devices can be avoided. But this scheme is to decompose N 2 The requirements of the O catalyst are extremely high, and the conditions for the O catalyst are extremely high: about 40000h -1 The space velocity of (2), the reaction temperature of 850 ℃, the water content of 17% and the NO content of 10% in the gas, only have high requirements on the activity and the selectivity of the catalyst, and the mechanical strength and the thermal stability of the catalyst. In addition, pt combustibles on noble metal meshes also precipitate on the catalyst and decompose the desired oxidation product NO, resulting in a significant drop in nitric acid yield.
Thus, a process for directly reacting N in the production of nitric acid was developed 2 O is purified and decomposed, when meeting the requirement of N 2 High-efficiency decomposition of O without affecting NO and NO 2 Is a problem to be solved.
Disclosure of Invention
In view of the above problems, the present invention provides a method for decomposing N in a nitric acid oxidizing furnace 2 The metal forming catalyst of O is obtained by carrying out the steps of high-temperature calcination pretreatment, auxiliary kneading forming and the like on a molecular sieve carrier, and then carrying out metal modification to obtain the forming catalyst with high catalytic activity, high mechanical strength and high temperature stability. The metal forming catalyst can not only meet the requirement of N 2 O is decomposed efficiently without affecting NO and NO 2 Plays a positive role in reducing the emission of waste gas in the nitric acid industry.
The technical scheme of the invention is as follows:
the invention provides a method for decomposing N 2 The metal forming catalyst of O comprises the following raw materials in parts by weight:
molecular sieve carrier: 70-100 parts by weight;
metal monoatoms: loading 1.0-5.0% of the molecular sieve carrier;
and (2) a binder: 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 monoatoms are selected from one or more than two of Cu, fe, zn, mg, ni, mn;
the water-powder ratio of the metal forming catalyst is 60-70 mL/g.
Further, the metal monoatoms are a combination of Cu and Fe or a combination of Fe, ni and Mg or a combination of Cu, zn and Mn. More preferably a combination of Cu, zn, mn.
Further, the loading of the metal atoms is 1.0% -5.0% based on the mass of the molecular sieve carrier.
Further, the particle size of the molecular sieve carrier is 100-150 meshes.
Further, the molecular sieve support has a silica to alumina ratio of 25 to 40, preferably 30 to 35, more preferably 30.
Further, the binder is one or more than two of pseudo-boehmite powder, acidic silica sol, aluminum oxide and the like.
Further, 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 68wt% nitric acid.
Further, the compressive strength of the metal forming catalyst is 90-150N/cm.
Further, in the final catalyst product of the invention, the extrusion aid, 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:
s1, step: preparation of shaped molecular sieve supports
S1-1: high-temperature calcination:
calcining the molecular sieve carrier, heating to 540-550 ℃ at a heating rate of 2-5 ℃/min, calcining at constant temperature for 6-10h after reaching the final temperature, and cooling to room temperature;
s1-2: pulverizing:
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, extruding, aging and extrusion molding the obtained mud-like material to obtain a molded molecular sieve carrier with a Raschig ring structure;
s1-4: drying and calcining the shaped molecular sieve carrier;
s2, step: and (3) dipping modification:
and measuring a certain amount of deionized water according to the saturated water absorption amount of the molded molecular sieve carrier, calculating the required metal salt mass, dissolving the metal salt into the deionized water, dropwise adding the metal salt solution into the molded molecular sieve carrier, continuously stirring the metal salt solution in the dropwise adding process to ensure that the metal salt solution is uniformly absorbed by the molded molecular sieve carrier, drying the molded molecular sieve carrier in a drying oven at the temperature of between 40 and 60 ℃ for 6 to 8 hours in a water bath at the temperature of between 100 and 120 ℃ for 8 to 10 hours, and calcining the molded molecular sieve carrier at the temperature of between 550 ℃ for 6 to 10 hours in a muffle furnace to obtain the final metal molded catalyst.
Further, in step S1-1, the aim of pretreating the molecular sieve carrier by high-temperature calcination before use is to remove volatile components in the molecular sieve by high-temperature decomposition, so that the finally formed catalyst maintains stable catalytic performance and can also improve the mechanical strength of the catalyst.
Further, in step S1-2, the conventional powdery or granular catalyst has the disadvantages of large pressure drop, easy reactor blockage and the like under the high fluid flow rate of the reaction, and cannot be directly applied to industrial production, so that the method disclosed by the invention is used for grinding and pulverizing the molecular sieve carrier after high-temperature calcination, and the particle size is controlled within a certain range, so that the molecular sieve carrier has a certain shape, particle size and industrial strength.
Further, in step S1-3, the binder and the extrusion aid are added into the molecular sieve carrier to be mixed, the peptizing agent is added into deionized water to prepare an acidic dilute solution, and finally the acidic alkene solution is added into powder to be fully kneaded, so that a mud-like material is obtained.
Further, in the step S1-3, the prepared mud-shaped material is extruded into mud blanks in a double-screw extruder with the extrusion rotating speed of 40-60 r/min, mud blank samples are placed in a shade and dry place for aging for 6-8h, and then the aged blanks are placed in an extrusion molding machine for extrusion molding by using a grinding tool, so that the molded molecular sieve carrier is obtained. Further, the molded molecular sieve carrier is 20 x 20mm, and the wall thickness is 3mm of the Raschig ring structured molded molecular sieve.
Further, in the step S1-4, the molded molecular sieve carrier is dried for 4-6 hours at 100-120 ℃ in a forced air drying box, then calcined for 6-8 hours at 550-650 ℃ in a muffle furnace, and naturally cooled to room temperature.
Further, in step S2, the metal salt is Cu 2+ 、Fe 2+ 、Zn 2+ 、Mg 2+ 、Ni 2+ 、Mn 2+ One or more of nitrate, sulfate or oxalate.
The technical scheme of the invention has the following beneficial effects:
(1) The metal forming catalyst of the invention enables N2O to be completely decomposed at high temperature, the conversion rate is 100%, and the metal forming catalyst does not react with NO;
(2) The metal forming catalyst of the invention has strong stability and can stably decompose N at 800-900 DEG C 2 O。
(3) The catalyst has better mechanical strength, can effectively support a platinum screen frame, and can not increase production energy consumption.
(4) The metal modified forming catalyst has good plasticity and is beneficial to successful extrusion forming of the catalyst.
Detailed Description
The present invention will be described in detail by way of examples, which are not intended to limit the scope of the present invention.
Example 1
A Fe/SSZ-16 shaped catalyst consists of the following raw materials:
molecular sieve carrier: SSZ-16, 75 parts by weight;
metal monoatoms: fe,1.923 parts by weight;
and (2) a binder: pseudo-boehmite powder, 25 parts by weight;
extrusion aid: sesbania powder, 3 parts by weight;
peptizing agent: nitric acid, 10 parts by weight;
the preparation method comprises the following steps:
s1-1: high-temperature calcination:
placing 200g of SSZ-16 molecular sieve in an evaporation dish, placing in a muffle furnace, heating from room temperature to 540 ℃ at a heating rate of 2 ℃/min, calcining at constant temperature for 6 hours, and naturally cooling to room temperature;
s1-2: pulverizing:
pulverizing the SSZ-16 molecular sieve subjected to high-temperature calcination, sieving, and controlling the particle size to 150 meshes to obtain a sieved SSZ-16 molecular sieve;
s1-3: dry blending, kneading and extrusion molding:
dry blending: weighing 75g of SSZ-16 molecular sieve, 25g of pseudo-boehmite powder and 3g of sesbania powder, putting the mixture into a mixer, stirring uniformly for 20-30 minutes, and controlling the temperature to be about 30 ℃;
kneading: adding 65ml of water and 10g of nitric acid (with the concentration of 68 wt%) into the mixed materials slowly and uniformly, stirring and kneading for 20-30 minutes, and controlling the temperature to be about 30 ℃;
extrusion molding: kneading the kneaded mud-like material into mud blanks in an F-26 double-screw extruder with the extrusion rotating speed of 50r/min, placing a mud blank sample in a shade and dry place for aging for 6 hours, and then placing the aged blanks in an extrusion molding machine for extrusion molding by using a grinding tool to prepare a molded catalyst with a 20 x 20mm Raschig ring structure and the wall thickness of 3 mm;
s1-4: drying and calcining the shaped molecular sieve carrier;
and (3) placing the extruded and molded molecular sieve carrier in a forced air drying oven to be dried continuously at 110 ℃ for 6 hours, then heating the molecular sieve carrier in a muffle furnace from room temperature to 550 ℃ at a heating rate of 2 ℃/min, calcining at constant temperature for 6 hours, and naturally cooling to room temperature.
S2: and (3) dipping modification:
with a metallic iron loading of 2.5%, 13.911g of ferric nitrate (Fe (NO 3 ) 3 ·3H 2 O) dissolving in 44g of deionized water to prepare an iron ion impregnating solution, slowly dripping the impregnating solution into a formed molecular sieve carrier, continuously stirring in the dripping process to ensure that the solution is uniformly absorbed by the carrier, drying in a drying oven at the constant temperature of 60 ℃ for 6h and at the temperature of 110 ℃ for 10h in a water bath, and calcining in a muffle furnace at the temperature of 550 ℃ for 6h to prepare the final required Fe/SSZ-16 formed catalyst with 20 x 20mm of loaded metallic iron and a raschig ring structure with the wall thickness of 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 monoatoms: 1.633 parts by weight of Cu;
and (2) a binder: 20 parts by weight of pseudo-boehmite powder;
extrusion aid: sesbania powder 2.5 weight portions;
peptizing agent: nitric acid, 10 parts by weight;
the preparation method comprises the following steps:
s1-1: high-temperature calcination:
placing 200g RUB-50 molecular sieve in an evaporation dish, placing in a muffle furnace, heating from room temperature to 540 ℃ at a heating rate of 2 ℃/min, calcining at constant temperature for 6 hours, and naturally cooling to room temperature;
s1-2: pulverizing:
pulverizing the RUB-50 molecular sieve subjected to high-temperature calcination, sieving, and controlling the particle size to 150 meshes to obtain a sieved RUB-50 molecular sieve;
s1-3: dry blending, kneading and extrusion molding:
dry blending: weighing 80g of RUB-50 molecular sieve, 20g of pseudo-boehmite powder and 2.5g of sesbania powder, putting into a mixer, stirring uniformly for 20-30 minutes, and controlling the temperature to be about 30 ℃;
kneading: 60ml of water and 10g of nitric acid (with the concentration of 68 weight percent) are slowly and uniformly added into the mixed materials, stirred and kneaded for 20 to 30 minutes, and the temperature is controlled to be about 30 ℃;
extrusion molding: kneading the kneaded mud-like material into mud blanks in an F-26 double-screw extruder with the extrusion rotating speed of 50r/min, placing a mud blank sample in a shade and dry place for aging for 8 hours, and then placing the aged blanks in an extrusion molding machine for extrusion molding by using a grinding tool to prepare a molded catalyst with a 20 x 20mm Raschig ring structure and the wall thickness of 3 mm;
s1-4: drying and calcining the shaped molecular sieve carrier;
continuously drying the extruded and molded molecular sieve carrier in a forced air drying oven at 120 ℃ for 4 hours, heating the molecular sieve carrier in a muffle furnace from room temperature to 550 ℃ at a heating rate of 2 ℃/min, calcining at constant temperature for 6 hours, and naturally cooling to room temperature;
s2: and (3) dipping modification:
copper metal loading was 2.0%, 6.2g copper nitrate (Cu (NO 3 ) 2 ·3H 2 O) dissolving in 43g of deionized water to prepare an iron ion impregnating solution, slowly dripping the impregnating solution into a formed molecular sieve carrier, continuously stirring in the dripping process to ensure that the solution is uniformly absorbed by the carrier, drying in a drying oven at the constant temperature of 60 ℃ for 6h and at the temperature of 110 ℃ for 8h in a water bath, and calcining in a muffle furnace at the temperature of 550 ℃ for 6h to prepare the final formed catalyst with 20 x 20mm of supported metal iron and a Raschig ring structure with the wall thickness of 3 mm.
Example 3
A Fe and Cu/SSZ-39 shaped catalyst consists of the following raw materials:
molecular sieve carrier: SSZ-39, 70 parts by weight;
metal monoatoms: fe and Cu are 1.066 parts by weight;
and (2) a binder: 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, is heated to 540 ℃ from room temperature at a heating rate of 2 ℃/min, is calcined at a constant temperature for 6 hours, and is naturally cooled to room temperature;
s1-2: pulverizing:
pulverizing the SSZ-39 molecular sieve subjected to high-temperature calcination, sieving, and controlling the particle size to 150 meshes to obtain a sieved SSZ-39 molecular sieve;
s1-3: dry blending, kneading and extrusion molding:
dry blending: weighing 70g of SSZ-39 molecular sieve, 30g of pseudo-boehmite powder and 3.5g of sesbania powder, putting into a mixer, stirring uniformly for 20-30 minutes, and controlling the temperature to be about 30 ℃;
kneading: slowly and uniformly adding 65ml of water and 13g of nitric acid (with the concentration of 68 wt%) into the above-mentioned mixed material, stirring and kneading for 20-30 min, and controlling its temperature at about 30 deg.C;
extrusion molding: kneading the kneaded mud-like material into mud blanks in an F-26 double-screw extruder with the extrusion rotating speed of 50r/min, placing a mud blank sample in a shade and dry place for aging for 8 hours, and then placing the aged blanks in an extrusion molding machine for extrusion molding by using a grinding tool to prepare a molded catalyst with a 20 x 20mm Raschig ring structure and the wall thickness of 3 mm;
s1-4: drying and calcining the shaped molecular sieve carrier;
continuously drying the extruded and molded molecular sieve carrier in a forced air drying oven at 110 ℃ for 4 hours, heating the molecular sieve carrier in a muffle furnace from room temperature to 550 ℃ at a heating rate of 2 ℃/min, calcining at constant temperature for 6 hours, and naturally cooling to room temperature;
s2: and (3) dipping modification:
the loading of metallic copper and iron was 1.5% each, and 8g of copper nitrate (Cu (NO 3 ) 2 ·3H 2 O) 11g of ferric nitrate (Fe (NO) 3 ) 3 ·3H 2 O) dissolving in 53g deionized water to prepare an iron ion impregnating solution, slowly dripping the impregnating solution into a formed molecular sieve carrier, continuously stirring in the dripping process to ensure that the solution is uniformly absorbed by the carrier, drying in a drying oven at the constant temperature of 60 ℃ for 6h and at the temperature of 110 ℃ for 8h in a water bath, and calcining in a muffle furnace at the temperature of 550 ℃ for 6h to prepare the final formed catalyst with 20 x 20mm of supported metallic copper and iron and a Raschig ring structure with the wall thickness of 3 mm.
Comparative example 1
In comparative example 1, the preparation procedure and formulation were the same as in example 1 except that the impregnation modification of step S-2 in example 1 was not performed, and a molded catalyst of an unmodified Raschig ring structure was finally obtained in comparative example 1.
Comparative example 2
In comparative example 2, the preparation procedure and formulation were the same as in example 2 except that the impregnation modification of step S-2 in example 2 was not performed, and a molded catalyst of unmodified Raschig ring structure was finally obtained in comparative example 2.
Comparative example 3
In comparative example 3, the preparation procedure and formulation were the same as in example 3 except that the impregnation modification of step S-3 in example 3 was not performed, and a molded catalyst of an unmodified Raschig ring structure was finally obtained in comparative example 3.
Test case
(1) The mechanical strength test method of the molded catalyst is as follows:
the shaped catalysts prepared in examples 1, 2, 3 and comparative examples 1, 2, 3 were subjected to strength detection using a DL ii type intelligent particle strength detector, each group was subjected to compressive strength detection by taking 20 sections of the same size catalyst, and finally, an average value was taken in N/cm.
(2) The molding catalyst plasticity test method comprises the following steps:
the plasticity is to determine the plasticity of the pug by researching the relation between stress and strain of a sample in the stressing process. The smaller the plasticity number, the better the plasticity of the catalyst blank, and conversely the worse the plasticity of the catalyst blank. The plasticity is an important index of 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 in the examples and the comparative examples were respectively prepared into cylindrical samples with F28 x 38mm, the cylindrical samples were placed in the center of a platen of a KS-B microcomputer plasticity tester, the cylindrical samples were continuously deformed with the continuous increase of the pressure on the platen, and the plasticity on the tester was read when the pressure of the platen was no longer increased.
The plasticity calculation method comprises the following steps:
wherein: r-the plasticity of the blank;
a-constant, which is 1.8 for a cylindrical sample of F28 x 38 mm;
F 10 -the pressure value at which the sample is compressed by 10%;
F 50 -pressure value at which the sample is compressed by 50%.
(3) The denitration activity test method of the formed catalyst comprises the following steps:
the activity evaluation device is a gas-solid phase catalytic reaction evaluation device. The molded catalyst was treated into a small test piece having a mass of 0.5g, and placed in a reaction tube. Introducing carrier gas He, adsorbing and balancing, and introducing 1000ppm NO and 1500ppm N 2 Mixture of O, O 2 The content was adjusted to 8.5%, and the reaction space velocity was set to 100000h -1 . The reaction was continued for 10h after the reaction temperature was raised from room temperature to 800℃and N was measured at 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, respectively 2 O and NO X The residual concentration of (2) is calculated according to a formula to obtain N 2 O、NO X Conversion rate.
Catalytic activity of shaped catalyst is defined by N 2 Conversion of O and NO X The conversion is reflected, and the calculation formula is as follows:
mechanical Strength, N of shaped catalysts prepared in the different examples and comparative examples 2 Conversion of O, NO X The conversion is shown in tables 1, 2 and 3.
Table 1 mechanical strength of shaped catalysts prepared in different examples and comparative examples
| Examples | 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 of Table 1, it is seen that the mechanical strength of the shaped catalyst modified by metal impregnation is significantly improved. Furthermore, as seen from a comparison of the mechanical strengths of examples 1 to 3, the mechanical strength of the molded catalyst supporting both metals was significantly improved over that of the molded catalyst supporting only one metal.
Table 2 plasticity of the shaped catalysts prepared in the different examples and comparative examples
| Examples | Plasticity degree |
| 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 molded catalyst obtained by metal impregnation modification has a plasticity value lower than that of the molded catalyst obtained by no metal impregnation modification, and has good plasticity, and the smoothness of the texture of the molded catalyst can be improved.
TABLE 3 differentN of shaped catalysts prepared in examples and comparative examples 2 Conversion of O
From the results in Table 3, it is seen that N of the shaped catalyst modified by metal impregnation 2 The conversion rate of O reaches 100 percent, and N is generated within 1h of the start of the catalytic reaction 2 O is completely decomposed;
while the shaped catalyst is not modified by metal impregnation N 2 The 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 are capable of stably decomposing N at 800-900 ℃C 2 And O, the stability is enhanced.
TABLE 4 NO of shaped catalysts prepared in different examples and comparative examples X Conversion rate
As seen from the results of 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 have not been modified by metal impregnation reacted with NO in the first few hours, it can be seen that the shaped catalysts of examples 1-3 do not affect the NO production, such that N is obtained 2 The selectivity of O is higher.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any other way, but is intended to cover any modifications or equivalent variations according to the technical spirit of the present invention, which fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. For decomposing N 2 The 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 monoatoms: loading 1.0-5.0% of the molecular sieve carrier;
and (2) a binder: 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 monoatoms are selected from one or more than two of Cu, fe, zn, mg, ni, mn;
the water-powder ratio of the metal forming catalyst is 60-70 mL/g;
the preparation method of the metal forming catalyst comprises the following steps:
s1, step: preparation of shaped molecular sieve supports
S1-1: high-temperature calcination:
calcining the molecular sieve carrier, heating to 540-550 ℃ at a heating rate of 2-5 ℃/min, calcining at constant temperature for 6-10h after reaching the final temperature, and cooling to room temperature;
s1-2: pulverizing:
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, extruding, aging and extrusion molding the obtained mud-like material to obtain a molded molecular sieve carrier with a Raschig ring structure;
s1-4: drying and calcining the shaped molecular sieve carrier;
s2, step: and (3) dipping modification:
and measuring a certain amount of deionized water according to the saturated water absorption amount of the molded molecular sieve carrier, calculating the required metal salt mass, dissolving the metal salt into the deionized water, dropwise adding the metal salt solution into the molded molecular sieve carrier, continuously stirring the metal salt solution in the dropwise adding process to ensure that the metal salt solution is uniformly absorbed by the molded molecular sieve carrier, drying the molded molecular sieve carrier in a drying oven at the temperature of between 40 and 60 ℃ for 6 to 8 hours in a water bath at the temperature of between 100 and 120 ℃ for 8 to 10 hours, and calcining the molded molecular sieve carrier at the temperature of between 550 ℃ for 6 to 10 hours in a muffle furnace to obtain the final metal molded catalyst.
2. The metal forming catalyst according to claim 1, wherein the metal monoatoms are a combination of Cu, fe or a combination of Fe, ni, mg or a combination of Cu, zn, mn.
3. The metal forming catalyst according to claim 2, wherein the loading of the metal atoms is 1.0 to 5.0% based on the mass of the molecular sieve support.
4. A 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 according to claim 4, wherein the extrusion aid is one or more of sesbania powder and glycerin polycarboxylic acid.
6. The metal forming 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 60wt% to 68wt%.
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 the metal forming catalyst according to any one of claims 1 to 7, comprising the steps of:
s1, step: preparation of shaped molecular sieve supports
S1-1: high-temperature calcination:
calcining the molecular sieve carrier, heating to 540-550 ℃ at a heating rate of 2-5 ℃/min, calcining at constant temperature for 6-10h after reaching the final temperature, and cooling to room temperature;
s1-2: pulverizing:
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, extruding, aging and extrusion molding the obtained mud-like material to obtain a molded molecular sieve carrier with a Raschig ring structure;
s1-4: drying and calcining the shaped molecular sieve carrier;
s2, step: and (3) dipping modification:
and measuring a certain amount of deionized water according to the saturated water absorption amount of the molded molecular sieve carrier, calculating the required metal salt mass, dissolving the metal salt into the deionized water, dropwise adding the metal salt solution into the molded molecular sieve carrier, continuously stirring the metal salt solution in the dropwise adding process to ensure that the metal salt solution is uniformly absorbed by the molded molecular sieve carrier, drying the molded molecular sieve carrier in a drying oven at the temperature of between 40 and 60 ℃ for 6 to 8 hours in a water bath at the temperature of between 100 and 120 ℃ for 8 to 10 hours, and calcining the molded molecular sieve carrier at the temperature of between 550 ℃ for 6 to 10 hours in a muffle furnace to obtain the final metal molded catalyst.
9. The method according to claim 8, wherein in step S1-3, the binder and the extrusion aid are added to the molecular sieve carrier to be mixed, the peptizing agent is added to deionized water to prepare an acidic dilute solution, and finally the acidic dilute solution is added to the mixed powder to be fully kneaded, so as to obtain the mud-like material.
10. The method according to claim 9, wherein in step S2, the metal salt is Cu 2+ 、Fe 2+ 、Zn 2+ 、Mg 2+ 、Ni 2+ 、Mn 2+ One or more of nitrate, sulfate or oxalate.
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