CN112337481A - Catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously and preparation method and application thereof - Google Patents
Catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously and preparation method and application thereof Download PDFInfo
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 117
- 229910052751 metal Inorganic materials 0.000 claims abstract description 115
- 239000013067 intermediate product Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000002156 mixing Methods 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 229910052593 corundum Inorganic materials 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 description 12
- 239000000725 suspension Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 229910017944 Ag—Cu Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 230000036541 health Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- -1 hydroxyl Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 241000894007 species Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
-
- 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
- B01D53/8634—Ammonia
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention relates to the technical field of atmosphere control, in particular to a catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously and a preparation method and application thereof. The preparation method comprises the following steps: soaking the carrier in a first metal precursor aqueous solution for first stirring, then carrying out first rotary evaporation to remove moisture in the obtained mixed material,drying and carrying out first roasting to obtain a first intermediate product; dipping the first intermediate product into a second metal precursor aqueous solution for second stirring, then performing second rotary evaporation to remove moisture in the obtained material, drying, and performing second roasting to obtain a second intermediate product; and reducing the second intermediate product to obtain the catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously. The catalyst can simultaneously and efficiently remove HCN and NH under the water-free atmosphere3。
Description
Technical Field
The invention relates to the technical field of atmosphere control, in particular to a catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously and a preparation method and application thereof.
Background
Hydrogen Cyanide (HCN) is a gaseous highly toxic substance, is a byproduct inevitably generated in most industrial production processes, and is one of the most typical unconventional toxic and harmful pollutants in industrial waste gases of phosphorus chemical industry, ammonia synthesis and coal chemical industry. Hydrogen Cyanide (HCN) and ammonia (NH) in industrial tail gas of phosphorus chemical industry and coal chemical industry3) The discharge of hydrogen cyanide into the atmosphere is frequently accompanied by a series of problems such as acid rain, ozone holes, greenhouse effect and the like, which are easy to threaten the lives of human beings and animals. Ammonia gas easily and strongly stimulates mucous membranes of eyes and respiratory tracts, and is also seriously harmful to the health of human beings and other living beings, and is an important precursor for forming dust haze in atmospheric environment. In recent years, the continuous development of various chemical industries directly leads to the rapid increase of the yield of hydrogen cyanide and ammonia gas in tail gas.
At present for the simultaneous removal of NH3And methods for HCN mainly include a liquid absorption method, an adsorption method, and the like. The liquid absorption method has relatively high treatment cost, unstable effect and easy generation of secondary pollution; the adsorption method essentially only transfers and enriches pollutants on the adsorption material, and HCN desorption caused by temperature change during the recovery of the adsorbent has secondary pollution hidden trouble and further threatens the life health of operators. In the current phase of research, the efficient HCN removal process is catalytic hydrolysis, while the mainstream NH3The purification method is catalytic oxidation. Although most catalysts are capable of catalyzing HCN and NH3However, the same catalyst needs different reaction conditions for catalyzing the two gases, for example, the water-containing condition can increase the removal efficiency of HCN, but can severely inhibit NH3And (4) oxidizing. The non-aqueous atmosphere has a high NH content3Catalytic activity, but the conversion of HCN is reduced.
Chinese patent CN111229210A discloses a catalyst with both HCN catalytic hydrolysis performance and NH performance3The catalyst with oxidizing performance uses hydrotalcite-like compound as catalyst, can efficiently hydrolyze HCN within the temperature range of 50-200 ℃, and can efficiently oxidize NH within the temperature range of 200-400 DEG C3The cost is low, the preparation is simple, but the HCN treatment effect is higher and NH is higher under the water-containing condition3Lower catalytic activity, in contrast to NH under anhydrous conditions3High conversion efficiency and low catalytic activity of HCN, so that the method cannot be applied to HCN and NH3While removing it.
Therefore, the development of a catalyst capable of efficiently catalytically oxidizing NH under the same reaction conditions3And HCN are necessary.
Disclosure of Invention
The invention aims to provide a catalyst capable of simultaneously removing hydrogen cyanide and ammonia gas, and a preparation method and application thereof3。
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously, which comprises the following steps:
soaking the carrier in a first metal precursor aqueous solution for first stirring, then carrying out first rotary evaporation to remove moisture in the obtained mixed material, drying, and carrying out first roasting to obtain a first intermediate product;
dipping the first intermediate product into a second metal precursor aqueous solution for second stirring, then performing second rotary evaporation to remove moisture in the obtained material, drying, and performing second roasting to obtain a second intermediate product;
reducing the second intermediate product to obtain a catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously;
the carrier is TiO2Nano gamma-Al2O3、CeO2One or more of ZSM-5, SAPO-34, SSZ-13 and Y-zeolite;
the metal in the first metal precursor aqueous solution and the second metal precursor aqueous solution is independently Cu, Fe, Mn, Ag, Co or Ni.
Preferably, the mass of the first metal in the first metal precursor aqueous solution and the mass of the second metal in the second metal precursor aqueous solution are independently 1 to 20% of the mass of the support.
Preferably, the temperature of the first roasting and the second roasting is independently 500-550 ℃, and the roasting time is independently 1-7 h.
Preferably, the first stirring and the second stirring are carried out at room temperature, and the time of the first stirring and the time of the second stirring are independently 2-12 h.
Preferably, the reduction treatment is performed in a mixed gas of hydrogen and nitrogen, and the hydrogen accounts for 10% by volume of the mixed gas.
Preferably, the temperature of the reduction treatment is 400-700 ℃, and the time is 1-4 h.
Preferably, the temperature of the first rotary evaporation and the temperature of the second rotary evaporation are 65-95 ℃ independently.
The invention provides a catalyst which is prepared by the preparation method in the scheme and can simultaneously remove hydrogen cyanide and ammonia gas, comprising a carrier and active components, wherein the active components are positioned in hydroxyl positions and pore channels of the carrier; the active component includes a first metal and a second metal; the particle size of the second metal is larger than that of the first metal; the first metal and the second metal are independently Cu, Fe, Mn, Ag, Co or Ni; the carrier is TiO2Nano gamma-Al2O3、CeO2ZSM-5, SAPO-34, SSZ-13 and Y-zeoliteOne or more of stones.
The invention provides application of the catalyst capable of simultaneously removing hydrogen cyanide and ammonia gas in the scheme in treatment of tail gas containing hydrogen cyanide and/or ammonia gas, and the application is carried out under anhydrous conditions.
Preferably, the method of application comprises: the catalyst is placed in a fixed bed, the fixed bed containing the catalyst is placed in tail gas containing hydrogen cyanide and/or ammonia gas for reaction, and the reaction temperature is 150-500 ℃.
The invention provides a preparation method of a catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously, which comprises the following steps: soaking the carrier in a first metal precursor aqueous solution for first stirring, then carrying out first rotary evaporation to remove moisture in the obtained mixed material, drying, and carrying out first roasting to obtain a first intermediate product; dipping the first intermediate product into a second metal precursor aqueous solution for second stirring, then performing second rotary evaporation to remove moisture in the obtained material, drying, and performing second roasting to obtain a second intermediate product; reducing the second intermediate product to obtain a catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously; the carrier is TiO2Nano gamma-Al2O3、CeO2One or more of ZSM-5, SAPO-34, SSZ-13 and Y-zeolite; the metal in the first metal precursor aqueous solution and the second metal precursor aqueous solution is independently Cu, Fe, Mn, Ag, Co or Ni.
The invention uses inorganic metal oxide or molecular sieve rich in hydroxyl as carrier, the number of hydroxyl directly determines the dispersibility of active metal and the particle size after reduction, and the first metal replaces a large number of hydroxyl to be loaded on the surface of the carrier through first impregnation and first roasting, at the moment, the first metal is in a state with high dispersibility and mostly exists in a metal monatomic oxide (namely, the active metal replaces hydroxyl to form [ active metal atom-O-carrier with other atoms except oxygen)]Form (e), a state in which no cluster is formed), the formation of metal oxide clusters is also small; when the second metal is loaded, the carrier does not have enough hydroxyl groups, so that the second roasting process can cause micropores of the carrierThe structure is agglomerated into a larger metal oxide, so that the dispersity of the two metals is different, and finally, most of the first metal monatomic oxide and the second metal oxide are reduced into metal simple substances through reduction treatment, but different dispersity can cause different particle sizes of metal simple substance particles loaded successively, and the different particle sizes are different for NH3Different from the adsorption capacity and the oxygen activation capacity of HCN, the metal elementary substance particles of the active component have different particle sizes, so that the catalyst can adsorb NH3The HCN and the HCN have good adsorption capacity and higher oxygen activating capacity, so that the HCN and the NH can be adsorbed under the same condition3Efficient removal of the active species. The invention activates O by active metal2Forming active oxygen with high activity, and further reacting with HCN and NH3The reaction achieves conversion of both species.
The catalyst prepared by the invention can simultaneously remove HCN and NH in various industrial tail gases3Reacting HCN and NH3Oxidation to water and N2At the maximum space velocity of 64200h-1Achieves 95 percent of HCN conversion rate and 100 percent of NH3Conversion, N2The selectivity can reach 95 percent.
In addition, the catalyst can be obtained only by dipping and simple roasting, and the method is simple and easy to implement; according to the invention, the inorganic metal oxide or molecular sieve rich in hydroxyl is used as a carrier, the cheap metal is used as an active component, and all reagent materials are relatively cheap in the preparation process of the catalyst, so that the preparation cost is low; the catalyst can remove HCN and NH simultaneously3In addition, it can also be in NH3Or tail gas with independent HCN exists is used, and the application range is wide.
Drawings
FIG. 1 shows the reaction temperature of the catalyst prepared in example 1 for HCN and NH3The conversion curve of (a);
FIG. 2 is a graph showing the effect of catalysts prepared by different carriers on ammonia removal.
Detailed Description
The invention provides a preparation method of a catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously, which comprises the following steps:
soaking the carrier in a first metal precursor aqueous solution for first stirring, then carrying out first rotary evaporation to remove moisture in the obtained mixed material, drying, and carrying out first roasting to obtain a first intermediate product;
dipping the first intermediate product into a second metal precursor aqueous solution for second stirring, then performing second rotary evaporation to remove moisture in the obtained material, drying, and performing second roasting to obtain a second intermediate product;
reducing the second intermediate product to obtain a catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously;
the carrier is TiO2Nano gamma-Al2O3、CeO2One or more of ZSM-5, SAPO-34, SSZ-13 and Y-zeolite;
the metal in the first metal precursor aqueous solution and the second metal precursor aqueous solution is independently Cu, Fe, Mn, Ag, Co or Ni.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The method comprises the steps of immersing a carrier in a first metal precursor aqueous solution for first stirring, then removing moisture in the obtained mixed material through first rotary evaporation, drying, and performing first roasting to obtain a first intermediate product.
In the present invention, the carrier is TiO2Nano gamma-Al2O3、CeO2One or more of ZSM-5, SAPO-34, SSZ-13 and Y-zeolite, preferably nano gamma-Al2O3. The invention takes the oxide or the molecular sieve rich in hydroxyl as the carrier of the active component, because the hydroxyl number directly determines the dispersibility and the reduced particle size of the active metal, the more the hydroxyl number of the carrier is rich, the higher the catalyst performance is, thus the nanometer gamma-Al rich in hydroxyl2O3Is the best carrier.
In the present invention, the first metal in the first metal precursor aqueous solution is preferably Cu, Fe, Mn, Ag, Co, or Ni, and more preferably Ag. The first metal precursor is not particularly limited in kind as long as it is completely soluble in water, such as nitrate, sulfate or chloride, and preferably nitrate of the first metal. In the invention, when the nitrate of the first metal is adopted as the first metal precursor, the catalytic performance of the obtained catalyst is better.
The concentration of the first metal precursor aqueous solution is not particularly required, and any concentration can be adopted, and a saturated solution is preferred. The invention has no special requirement on the dosage of the first metal precursor aqueous solution, and can completely immerse the carrier.
In the present invention, the mass of the first metal in the first metal precursor aqueous solution is preferably 1 to 20% of the mass of the support, more preferably 5 to 15%, even more preferably 7 to 12%, and most preferably 10%.
In the present invention, the first stirring is preferably performed at room temperature, and the time of the first stirring is preferably 1 to 12 hours, such as 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours or 12 hours, and preferably 2 hours. The rate of the first agitation is not particularly critical to the present invention and may be any rate known in the art.
The invention utilizes the first stirring to realize the full mixing of the carrier and the first metal ions.
After the first stirring is finished, the method carries out first rotary evaporation, removes water in the obtained mixed material, and then carries out drying.
In the invention, the temperature of the first rotary evaporation is preferably 65-95 ℃, more preferably 70-90 ℃, and most preferably 80 ℃. In the invention, the drying temperature is preferably 90-110 ℃, and more preferably 105 ℃; the drying time is preferably 6-12 h, and more preferably 10 h.
After the drying is finished, the invention carries out first roasting on the obtained dried material to obtain a first intermediate product. In the invention, the temperature of the first roasting is preferably 500-550 ℃, and more preferably 550 ℃; the roasting time is preferably 1-7 h, and more preferably 3 h. In the present invention, the first firing is preferably performed in an air atmosphere. The temperature of the invention is preferably raised from room temperature to the temperature of the first calcination, and the temperature raising rate is preferably 0.5 ℃/min.In the first roasting process, the crystal form of the carrier grows, and meanwhile, first metal ions fully mixed with the carrier replace hydroxyl hydrogen to form an X-O-M structure linked on the carrier, so that the load of the active metal is realized, wherein X is a first metal atom, M is other atoms except oxygen of the carrier, generally is a carrier metal atom, such as nano gamma-Al2O3On the surface of which an X-O-Al structure is formed, on the TiO2The structure of X-O-Ti is formed, and the structures of X-O-Al and X-O-Si are formed on ZSM-5.
After the first intermediate product is obtained, the first intermediate product is soaked in a second metal precursor aqueous solution for second stirring, then the moisture in the obtained material is removed through second rotary evaporation, and the second intermediate product is obtained through drying and second roasting.
In the present invention, the second metal in the second metal precursor aqueous solution is preferably Cu, Fe, Mn, Ag, Co, or Ni, and more preferably Cu. In the invention, the first metal is Ag, and the second metal is Cu, so that the effect of removing hydrogen cyanide and ammonia gas is better.
The second metal precursor is not particularly limited in kind as long as it is completely soluble in water, such as nitrate, sulfate or chloride, and preferably nitrate of the second metal. In the invention, when the second metal precursor adopts the nitrate of the second metal, the catalytic performance of the obtained catalyst is better.
The concentration of the second metal precursor aqueous solution is not particularly required, and any concentration can be adopted, and a saturated solution is preferred. The invention has no special requirement on the dosage of the second metal precursor aqueous solution, and the first intermediate product can be completely immersed.
In the present invention, the mass of the second metal in the second metal precursor aqueous solution is preferably 1 to 20% of the mass of the support, more preferably 5 to 15%, even more preferably 7 to 12%, and most preferably 10% of the mass of the support, based on the mass of the support used for preparing the first intermediate product.
In the present invention, the second stirring condition is the same as the first stirring condition, and is not described herein again. The invention utilizes the second stirring to realize the full mixing of the second metal ions and the first intermediate.
After the second stirring is finished, the method carries out second rotary evaporation, removes the moisture in the obtained material and then carries out drying.
In the present invention, the conditions of the second rotary evaporation are the same as the conditions of the first rotary evaporation, and the drying conditions are the same as the drying conditions after the first rotary evaporation, which are not described herein again.
After the drying is finished, the product obtained by drying is subjected to second roasting to obtain a second intermediate product. In the present invention, the conditions of the second firing are the same as those of the first firing. Because a large amount of hydroxyl groups on the carrier are occupied by the first metal after the first roasting, the first metal cannot be changed in the second roasting process, and the second metal cannot be connected with the carrier due to insufficient hydroxyl point positions, so that the second metal ions start to agglomerate to form large-particle metal oxides to stay in microchannels of the carrier, and the dispersion degree of the second metal compared with the first metal is greatly reduced.
After the second intermediate product is obtained, the second intermediate product is subjected to reduction treatment to obtain the catalyst capable of simultaneously removing hydrogen cyanide and ammonia gas.
In the present invention, the reduction treatment is preferably performed in a mixed gas of hydrogen and nitrogen, and the hydrogen is preferably 10% by volume of the mixed gas. In the invention, the temperature of the reduction treatment is preferably 400-700 ℃, more preferably 550-650 ℃, and most preferably 600 ℃; the time of the reduction treatment is preferably 1 to 4 hours, and more preferably 2 to 3 hours.
In the reduction treatment process, the monatomic oxide of the first metal is gathered and releases hydroxyl, the adsorption capacity to ammonia is enhanced due to the increase of hydroxyl sites, meanwhile, most of the monatomic oxide of the first metal and the oxide of the second metal are reduced into metal simple substance particles, only a small part of the first metal existing in the monatomic form and the oxide of the second metal exist in the finally reduced catalyst, the rest are metal simple substance particles with a certain particle size, and the simple substance particles of the second metal are larger than the simple substance particles of the first metal.
The invention provides a catalyst which is prepared by the preparation method in the scheme and can simultaneously remove hydrogen cyanide and ammonia gas, comprising a carrier and active components, wherein the active components are positioned in hydroxyl positions and pore channels of the carrier; the active component includes a first metal and a second metal; the particle size of the second metal is larger than that of the first metal; the first metal and the second metal are independently Cu, Fe, Mn, Ag, Co or Ni; the carrier is TiO2Nano gamma-Al2O3、CeO2One or more of ZSM-5, SAPO-34, SSZ-13 and Y-zeolite. In the present invention, the support is preferably nano γ -Al2O3The first metal is preferably Ag, and the second metal is preferably Cu. In the invention, the first metal is specifically positioned at the hydroxyl sites of the carrier, and a small part of the second metal is positioned at the hydroxyl sites of the carrier and a large part of the second metal is positioned in the pore channels of the carrier.
The first metal and the second metal simple substance particles have different particle sizes, and the different particle sizes are used for NH3Different from the adsorption capacity and the oxygen activation capacity of HCN, the metal elementary substance particles of the active component have different particle sizes, so that the catalyst can adsorb NH3The HCN and the HCN have good adsorption capacity and higher oxygen activating capacity, so that the HCN and the NH can be adsorbed under the same condition3Efficient removal of the active species. The invention activates O by active metal2Forming active oxygen with high activity, and further reacting with HCN and NH3The reaction achieves conversion of both species.
According to the catalyst, the first metal and the second metal simple substance particles have strong oxygen binding capacity, and the bound oxygen can be combined with H (hydrogen cyanide) removed to form water, so that metal atoms on the surfaces of the metal particles are always circulated between the simple substances and the metal oxide substances, and the catalyst is always stable.
The invention provides application of the catalyst capable of simultaneously removing hydrogen cyanide and ammonia gas in the scheme in treatment of tail gas containing hydrogen cyanide and/or ammonia gas, and the application is carried out under anhydrous conditions.
In the present invention, the method of application preferably comprises: the catalyst is placed in a fixed bed, and the fixed bed containing the catalyst is placed in tail gas containing hydrogen cyanide and/or ammonia gas for reaction.
In the invention, the particle size of the catalyst is preferably 40-60 meshes. The fixed bed is not particularly limited in the present invention, and a fixed bed known in the art may be used.
The invention has no special requirements on the concentration of hydrogen cyanide and ammonia gas in the tail gas, and the concentration is uniform at will. In the embodiment of the invention, the concentration of HCN in the tail gas is 200ppm (the state requires 200ppm of upper limit of the concentration of HCN gas for experiment), and the concentration of ammonia in the tail gas is 500 ppm.
In the invention, the reaction temperature is preferably 150-500 ℃, more preferably 225-450 ℃, more preferably 250-350 ℃, and most preferably 250 ℃; the volume space velocity of the reaction is preferably 118000h-1. In the present invention, O is preferably used2And N2The mixed gas of (1) as an equilibrium atmosphere, the mixed gas containing O2The content of (b) is preferably 10% by volume.
The catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously provided by the present invention, and the preparation method and application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking 10g of nano gamma-Al2O3With saturated AgNO3Mixing the solutions to make the atomic mass of the loaded Ag be 1g, stirring the mixed suspension for 2h at room temperature, performing first rotary evaporation at 65 ℃ to remove excessive water, drying at 105 ℃ for 10h, performing first roasting on the obtained sample at 550 ℃ in air atmosphere for 3h to obtain a first intermediate product which is Ag/Al2O3；
Mixing the first intermediate product with saturated Cu (NO)3)2Mixing the solutions until the added Cu atom mass is 1g, stirring the mixed suspension at room temperature for 2 hr, and performing second rotary evaporation at 65 deg.C to remove excessive Cu atomsDrying at 105 ℃ for 10h after moisture is removed, and roasting the obtained sample at 550 ℃ for 3h in air atmosphere to obtain a second intermediate product, namely Ag-Cu/Al2O3；
The second intermediate product is reacted in H2And N2Mixed atmosphere (H)2 Volume content 10%) for 2h at a temperature of 600 deg.c, to complete the preparation of the desired catalyst.
Example 2
Taking 20g of nano gamma-Al2O3With saturated AgNO3Mixing the solutions to make the atomic mass of the loaded Ag be 2g, stirring the mixed suspension for 3h at room temperature, performing first rotary evaporation at 85 ℃ to remove excessive water, drying at 105 ℃ for 10h, performing first roasting on the obtained sample at 500 ℃ in air atmosphere for 3h to obtain a first intermediate product which is Ag/Al2O3；
Mixing the first intermediate product with saturated Cu (NO)3)2Mixing the solutions to make the added Cu atomic mass be 1g, stirring the mixed suspension for 2h at room temperature, performing second rotary evaporation at 65 ℃ to remove excessive water, drying at 105 ℃ for 10h, performing second roasting on the obtained sample at 500 ℃ in air atmosphere for 3h to obtain a second intermediate product, namely Ag-Cu/Al2O3；
The second intermediate product is reacted in H2And N2Mixed atmosphere (H)2 Volume content 10%) for 2h at a temperature of 600 deg.c, to complete the preparation of the desired catalyst.
Example 3
Taking 20g of nano gamma-Al2O3With saturated AgNO3Mixing the solutions to make the atomic mass of the loaded Ag be 4g, stirring the mixed suspension for 3h at room temperature, performing first rotary evaporation at 85 ℃ to remove excessive water, drying at 105 ℃ for 10h, performing first roasting on the obtained sample at 500 ℃ in air atmosphere for 4h to obtain a first intermediate product, namely Ag/Al2O3；
Will be prepared toAn intermediate product and saturated Cu (NO)3)2Mixing the metal precursor solutions to enable the added Cu atomic mass to be 1g, stirring the mixed suspension for 2h at room temperature for the second time, performing second rotary evaporation at 85 ℃ to remove excessive water, drying at 105 ℃ for 10h, performing second roasting on the obtained sample at 500 ℃ in an air atmosphere for 4h to obtain a second intermediate product, namely Ag-Cu/Al2O3；
The second intermediate product is reacted in H2And N2Mixed atmosphere (H)2 Volume content 10%) for 2h at a temperature of 600 deg.c, to complete the preparation of the desired catalyst.
Example 4
Taking 20g of nano gamma-Al2O3With AgNO3Mixing the solutions to make the atomic mass of the loaded Ag be 4g, stirring the mixed suspension for 5h at room temperature, performing first rotary evaporation at 85 ℃ to remove excessive water, drying at 105 ℃ for 12h, performing first roasting on the obtained sample at 500 ℃ in an air atmosphere for 4h to obtain a first intermediate product, namely Ag/Al2O3；
Mixing the first intermediate product with saturated Cu (NO)3)2Mixing the solutions to make the added Cu atomic mass be 0.5g, stirring the mixed suspension for 2h at room temperature, performing second rotary evaporation at 85 ℃ to remove excessive water, drying at 105 ℃ for 10h, performing second roasting on the obtained sample at 500 ℃ in air atmosphere for 4h to obtain a second intermediate product, namely Ag-Cu/Al2O3；
The second intermediate product is reacted in H2And N2Mixed atmosphere (H)2 Volume content 10%) for 2h at a temperature of 700 deg.c, to complete the preparation of the desired catalyst.
Comparative example 1
The difference from the embodiment 1 is that only one-time load is adopted, and the specific steps are as follows:
10g of nano gamma-Al is taken2O3Saturated AgNO3Solution with saturated Cu (NO)3)2Mixing the solutions to ensure that the atomic mass of the loaded Ag is 1g and the atomic mass of the added Cu is 1g, stirring the mixed suspension for 2h at room temperature for the first time, then drying the suspension at 105 ℃ for 10h after removing excessive water through the first rotary evaporation at 65 ℃, and roasting the dried sample for 3h at 550 ℃ in an air atmosphere to obtain a first intermediate product, namely Ag-Cu/Al2O3；
The first intermediate product is reacted in H2And N2Mixed atmosphere (H)2 Volume content 10%) for 2h at a temperature of 600 deg.c, to complete the preparation of the desired catalyst.
And (3) performance testing:
1. the catalyst prepared in example 1 was used for the treatment of a catalyst containing both HCN and NH3In which the concentration of HCN is 100ppm, NH3The concentration of (2) was 500 ppm.
The reaction conditions are as follows: o is2And N2As an equilibrium atmosphere (wherein O is contained in the mixed gas)2Volume content of 10%) and a volume space velocity of 118000h-1The reaction temperatures were 100 ℃, 125 ℃, 150 ℃, 175 ℃, 200 ℃, 225 ℃, 250 ℃, 275 ℃ and 300 ℃ respectively, and the results are shown in FIG. 1.
As can be seen from FIG. 1, the catalyst prepared in example 1 was able to treat about 95% HCN and 80% NH at 225 deg.C3For simultaneous removal of HCN and NH3Has good treatment effect.
Whereas the catalyst prepared in comparative example 1 was exposed to HCN and NH at 225 ℃ under the same conditions3The removal rates of (A) and (B) are 40% and 100%, respectively, only for NH3Has higher removal rate, which shows that the invention can realize the reaction of HCN and NH under the same condition by secondary load roasting3While at the same time removing efficiently.
2. Screening of nano gamma-Al2O3And micron gamma-Al2O3The preparation of the catalyst is carried out by adopting the following methods respectively as a carrier: taking 10g of carrier and saturated AgNO3The solutions were mixed so that the atomic mass of Ag supported was 1g, and the mixed suspension was stirred at room temperature for 3 hours and then heated at 85 ℃ to prepare a gelRotary evaporating under the part to remove excessive water, drying at 105 deg.C for 10h, calcining the obtained sample at 500 deg.C in air atmosphere for 4h to obtain Ag/Al2O3(ii) a Mixing Ag with Al2O3In H2And N2Mixed atmosphere (H)2Volume content of 10%) at 500 deg.C for 2 hr.
The two catalysts obtained are used for treating NH-containing3Tail gas of (1), NH in the tail gas3The concentration of (B) is 500 ppm; the reaction conditions are as follows: o is2And N2As an equilibrium atmosphere (wherein O is contained in the mixed gas)2Volume content of 10%) and a volume space velocity of 118000h-1。
FIG. 2 is a diagram showing the effect of catalysts prepared by different carriers on removing ammonia, and it can be seen from FIG. 2 that nano gamma-Al2O3Relatively micron gamma-Al2O3The catalyst prepared by the catalyst as a carrier has better catalytic performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously is characterized by comprising the following steps:
soaking the carrier in a first metal precursor aqueous solution for first stirring, then carrying out first rotary evaporation to remove moisture in the obtained mixed material, drying, and carrying out first roasting to obtain a first intermediate product;
dipping the first intermediate product into a second metal precursor aqueous solution for second stirring, then performing second rotary evaporation to remove moisture in the obtained material, drying, and performing second roasting to obtain a second intermediate product;
reducing the second intermediate product to obtain a catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously;
the carrier is TiO2Nano gamma-Al2O3、CeO2One or more of ZSM-5, SAPO-34, SSZ-13 and Y-zeolite;
the metal in the first metal precursor aqueous solution and the second metal precursor aqueous solution is independently Cu, Fe, Mn, Ag, Co or Ni.
2. The method according to claim 1, wherein the mass of the first metal in the first metal precursor aqueous solution and the mass of the second metal in the second metal precursor aqueous solution are independently 1 to 20% of the mass of the support.
3. The method of claim 1, wherein the first and second baking temperatures are independently 500 to 550 ℃ and the baking time is independently 1 to 7 hours.
4. The method according to claim 1, wherein the first stirring and the second stirring are performed at room temperature, and the time for the first stirring and the time for the second stirring are independently 2 to 12 hours.
5. The production method according to claim 1, wherein the reduction treatment is performed in a mixed gas of hydrogen and nitrogen, and the hydrogen is 10% by volume of the mixed gas.
6. The method according to claim 5, wherein the reduction treatment is carried out at a temperature of 400 to 700 ℃ for 1 to 4 hours.
7. The preparation method according to claim 1, wherein the temperatures of the first rotary evaporation and the second rotary evaporation are 65-95 ℃ independently.
8. The catalyst prepared by the preparation method of any one of claims 1 to 7 and capable of removing hydrogen cyanide and ammonia gas simultaneously comprises a carrier and an active component, wherein the active component is positioned in the carrierHydroxyl sites and pore channels of the carrier; the active component includes a first metal and a second metal; the particle size of the second metal is larger than that of the first metal; the first metal and the second metal are independently Cu, Fe, Mn, Ag, Co or Ni; the carrier is TiO2Nano gamma-Al2O3、CeO2One or more of ZSM-5, SAPO-34, SSZ-13 and Y-zeolite.
9. Use of a catalyst capable of simultaneously removing hydrogen cyanide and ammonia gas according to claim 8 for the treatment of a tail gas containing hydrogen cyanide and/or ammonia gas, said use being carried out under anhydrous conditions.
10. The application according to claim 9, wherein the method of applying comprises: the catalyst is placed in a fixed bed, the fixed bed containing the catalyst is placed in tail gas containing hydrogen cyanide and/or ammonia gas for reaction, and the reaction temperature is 150-500 ℃.
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