Mn-HAP SCR Catalyst: Preparation and Sulfur Resistance

doi:10.15541/jim20220020

Abstract

Abstract:

Low-temperature selective catalytic reduction (SCR) denitrification is an important technology for the end treatment of flue gas and enhancing sulfur resistance of catalysts is a challenge demanding prompt solution in the field of low-temperature SCR. Here, a Mn-HAP catalyst for nitrogen removal at low temperature (100-200 ℃) was successfully synthesized by co-precipitation method using hydroxyapatite (HAP) as carrier and Mn as an active component, and then its denitrification performance and resistance to fight against metal sulfate and ammonium sulfate poisoning were studied. The results showed that the sulfur resistance of the catalyst could be improved to a certain extent by using HAP as Mn active substance carrier. When the reaction temperature was 140 ℃, the denitrification efficiency of the SCR catalyst reached 100%. Meanwhile, the effect of metal sulfate on the denitrification activity at low temperature was more significant than that of ammonium sulfate, and the denitrification efficiency under the two sulfate species at 120 ℃ was reduced by 37.40% and 8.83%, respectively, as compared with that of fresh catalyst. Different characterization analysis indicated that different surface sulfur species could reduce the specific surface area and change the oxidation state of active Mn to various degrees. The main reason for catalysts deactivation is that the metal sulfate can significantly decrease the proportion and oxidation-reduction performance of Mn⁴⁺. Therefore, this study provides an important direction for improving the sulfur resistance of SCR catalysts.

Key words: hydroxyapatite, low-temperature NH₃-SCR, SO₂ resistance, metal sulfate, ammonium sulfate

CLC Number:

TB34

CHEN Yaling, SHU Song, WANG Shaoxin, LI Jianjun. Mn-HAP SCR Catalyst: Preparation and Sulfur Resistance[J]. Journal of Inorganic Materials, 2022, 37(10): 1065-1072.

Figures/Tables 10

Fig. 1 Schematic illustration for preparing and poisoning catalysts

Fig. 2 Schematic illustration of denitration activity evaluation device

Fig. 3 (a) SCR activity of CPF, CPM, CPA, and HAP, and sulfur resistance test of CPF and (b) stability test of CPF Colorful figures are available on website

Table 1 Activity comparison of different catalysts

Catalyst	Preparation method	NO conversion/%	Temperature and condition	Ref.
Mn-HAP	Co-preparation	62.60	140 ℃, 200×10^-6 SO₂, 2 h	This research
NB-C-P	Hydrothermal	45.00	150 ℃, 250×10^-6 SO₂, 2 h	[20]
MnO₂	Oxalic acid co-precipitation	17.65	150 ℃, 200×10^-6 SO₂, 2 h	[21]
MnCrO_x	Hydrothermal redox reaction	37.46	150 ℃, 50×10^-6 SO₂, 2 h	[22]

Fig. 4 (a) XRD patterns and (b) DTG curves of catalysts

Fig. 5 (a) N2 adsorption-desorption isotherms and (b) pore size distributions of CPF, CPM, and CP

Table 2 Physical parameters of fresh catalysts and toxic catalysts

Sample	Specific area/ (m²·g^-1)	Pore volume/ (cm³·g^-1)	Average pore size/nm
CPF	153.6	0.5500	13.49
CPM	117.3	0.4600	14.11
CPA	133.2	0.4300	11.57

Fig. 6 (a) Mn2p and (b) O1s XPS spectra of CPF, CPM and CPA

Table 3 XPS results of Mn and O on the surface of fresh catalysts and toxic catalysts

Sample	O			Mn
Sample	O_latt/O	O_ads/O	O_ads/O_latt	Mn²⁺/Mn	Mn³⁺/Mn	Mn⁴⁺/Mn
CPF	0.9050	0.0950	0.1050	0.06510	0.1670	0.7300
CPM	0.9210	0.0790	0.0860	0.10000	0.5900	0.3100
CPA	0.8760	0.1230	0.1410	0.13500	0.2240	0.6410

Fig. 7 (a) H2-TPR and (b) NH3-TPD curves of CPF, CPM and CPA

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