CN111389419B - Cerium dioxide loaded ferric sulfate catalyst and preparation method and application thereof - Google Patents

Cerium dioxide loaded ferric sulfate catalyst and preparation method and application thereof Download PDF

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CN111389419B
CN111389419B CN202010245711.0A CN202010245711A CN111389419B CN 111389419 B CN111389419 B CN 111389419B CN 202010245711 A CN202010245711 A CN 202010245711A CN 111389419 B CN111389419 B CN 111389419B
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刘志明
周子正
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Beijing University of Chemical Technology
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • 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
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    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
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    • B01D2251/2062—Ammonia

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Abstract

Cerium dioxide loaded ferric sulfate catalyst and preparation method and application thereof belong to the technical field of environmental catalysis and atmospheric pollution control. The catalyst is prepared by adopting an impregnation method, cerium dioxide is used as a carrier, and ferric sulfate is used as an active component. It is characterized in that high-toxicity vanadium is not adopted as an active component, and simultaneously, the temperature is within 300-400 ℃, and the airspeed is 118000h‑1When the catalyst is used, the conversion rate of nitrogen oxides is over 90 percent, and the catalyst has good alkali metal resistance. The catalyst can be used for NO in fixed source flue gas and diesel vehicle tail gasxThe removal is efficient.

Description

Cerium dioxide loaded ferric sulfate catalyst and preparation method and application thereof
Technical Field
The invention relates to Selective Catalytic Reduction (SCR) NO for ammonia gasxThe cerium dioxide supported ferric sulfate catalyst is suitable for the emission of NO in waste gas of biomass boilers, coal-fired power plants, building material furnaces, steel smelting and other stationary sources and diesel vehicles and other mobile sourcesxBelonging to the technical field of environmental catalysis and atmospheric pollution control.
Background
Nitrogen Oxides (NO)x) Can cause environmental problems of acid rain, photochemical smog and the like, and causes great harm to human health, so NOxThe control of (2) is receiving wide attention. NH (NH)3SCR as NOxThe core technology of the effective technical means of removal is a high-efficiency and stable denitration catalyst. At present, conventional NH3SCR denitration catalyst predominantly V2O5-WO3(MoO3)/TiO2The catalyst has the following problems: active component V2O5Has biotoxicity, so that the cost for treating the waste catalyst is increased; the catalyst has poor alkali metal resistance; support TiO2The phase transition (from anatase to rutile) is easy to occur at high temperature, resulting in a significant decrease in the catalyst activity. Therefore, efficient and environmentally friendly NH was developed3SCR catalysts are a hotspot of academic and industrial research.
The invention is realized by adding CeO2Adding Fe2(SO4)3Preparing a para-NOxRemoving the novel non-vanadium denitration catalyst with good catalytic performance.
Disclosure of Invention
The invention aims to provide a method for preparing the catalyst with simple preparation process and selective reduction on ammoniaNOxA composite catalyst with high activity and good alkali-resistant performance and a preparation method thereof. In the cerium dioxide loaded ferric sulfate catalyst, ferric sulfate is highly dispersed in CeO2The surface (as shown in figure 1) and strong synergistic effect exists between cerium dioxide and ferric sulfate, the synergistic effect not only improves the oxidation-reduction property of the catalyst, but also obviously improves the acidity of the surface of the catalyst, and the improvement of the oxidation-reduction property and the acidity enables the catalyst to have excellent denitration activity and strong alkali metal resistance. Thereby preparing the composite denitration catalyst which is environment-friendly, high in denitration activity and strong in alkali metal resistance.
The purpose of the invention is realized by the following technical scheme:
cerium dioxide is used as a carrier, ferric sulfate is used as an active component, and the composition of the active component is expressed as Fe2(SO4)3/CeO2The mass percentage of ferric sulfate is 2% -10%.
The invention provides a method for preparing a cerium dioxide loaded ferric sulfate catalyst, which is characterized by sequentially comprising the following steps of:
(1) preparing 0.05-0.20 mol/L ferric sulfate solution;
(2) roasting cerium nitrate in a muffle furnace at 550 ℃ for 4 hours to prepare cerium dioxide;
(3) adding deionized water into the ferric sulfate solution obtained in the step (1), and uniformly stirring at room temperature to obtain the ferric sulfate solution
(2) Adding the obtained cerium dioxide into the solution, and stirring for 4-8 hours to obtain slurry;
(4) drying the slurry prepared in the step (3) at 120 ℃ for 12-24 hours to prepare a dried sample; placing the sample in a muffle furnace to be roasted for 4-8 hours at 500 ℃ to prepare Fe2(SO4)3/CeO2A catalyst.
Compared with the prior art, the invention has the following advantages and prominent effects: without the use of toxic active ingredients V2O5By adding to CeO2Adding Fe to the catalyst2(SO4)3，Fe2(SO4)3Highly dispersed in CeO2Surface, using CeO2With Fe2(SO4)3Due to the synergistic effect, the activity and alkali metal resistance of the catalyst are effectively improved, the denitration efficiency is good, and the purification efficiency of the nitric oxide is over 90% within the range of 300-400 ℃.
Drawings
FIG. 1.Fe2(SO4)3/CeO2And CeO2XRD spectrum of catalyst
Detailed Description
The technical scheme of the invention is further explained by combining the embodiment as follows:
example 1: 2% Fe2(SO4)3/CeO2Preparation of composite catalyst
a) 10g of cerium nitrate is taken to be roasted for 4 hours in a muffle furnace at the temperature of 550 ℃ to prepare cerium dioxide;
b) adding deionized water into 2.04ml of 0.05mol/L ferric sulfate solution, and uniformly stirring; adding 2g of the cerium dioxide obtained in the step a) into the solution, and stirring for 4 hours to prepare slurry;
c) drying the slurry prepared in the step (b) at 120 ℃ for 12 hours to prepare a dried sample; placing the sample in a muffle furnace to be roasted for 4 hours at the temperature of 500 ℃ to prepare 2% Fe2(SO4)3/CeO2A catalyst.
Example 2: 4% Fe2(SO4)3/CeO2Preparation of composite catalyst
a) 10g of cerium nitrate is taken to be roasted for 4 hours in a muffle furnace at the temperature of 550 ℃ to prepare cerium dioxide;
b) adding deionized water into 4.17ml of 0.05mol/L ferric sulfate solution, and uniformly stirring; adding 2g of the cerium dioxide obtained in the step a) into the solution, and stirring for 8 hours to prepare slurry;
c) drying the slurry prepared in the step (b) for 24 hours at the temperature of 120 ℃ to prepare a dried sample; the sample is placed in a muffle furnace to be roasted for 8 hours at the temperature of 500 ℃ to prepare 4 percent Fe2(SO4)3/CeO2A catalyst.
Example 3: 6% Fe2(SO4)3/CeO2Preparation of composite catalyst
a) 10g of cerium nitrate is taken to be roasted for 4 hours in a muffle furnace at the temperature of 550 ℃ to prepare cerium dioxide;
b) 3.19ml of 0.1mol/L ferric sulfate solution is taken, added with deionized water and stirred uniformly; adding 2g of the cerium dioxide obtained in the step a) into the solution, and stirring for 6 hours to prepare slurry;
c) drying the slurry prepared in the step (b) for 16 hours at the temperature of 120 ℃ to prepare a dried sample; placing the sample in a muffle furnace to be roasted for 6 hours at the temperature of 500 ℃ to prepare 6% Fe2(SO4)3/CeO2A catalyst.
Example 4: 10% Fe2(SO4)3/CeO2Preparation of composite catalyst
a) 10g of cerium nitrate is taken to be roasted for 4 hours in a muffle furnace at the temperature of 550 ℃ to prepare cerium dioxide;
b) adding deionized water into 2.78ml of 0.20mol/L ferric sulfate solution, and uniformly stirring; adding 2g of the cerium dioxide obtained in the step a) into the solution, and stirring for 8 hours to prepare slurry;
c) drying the slurry prepared in the step (b) for 16 hours at the temperature of 120 ℃ to prepare a dried sample; the sample is placed in a muffle furnace to be roasted for 6 hours at the temperature of 500 ℃ to prepare 10 percent Fe2(SO4)3CeO catalyst.
Example 5: 1% K/6% Fe2(SO4)3/CeO2Preparation of composite catalyst
a) 4.28ml of 0.1mol/L potassium nitrate solution is added with deionized water and stirred evenly; 2g of 6% Fe2(SO4)3/CeO2(preparation method is the same as example 3) is added into the solution and stirred for 6 hours to prepare slurry;
b) drying the slurry prepared in the step a) at 120 ℃ for 12 hours to prepare a dried sample. The sample was calcined in a muffle furnace at 500 c for 4 hours,to obtain 1% K/6% Fe2(SO4)3/CeO2A catalyst.
Example 6 (reference): CeO (CeO)2Preparation of the catalyst
10g of cerium nitrate is taken and roasted in a muffle furnace for 4 hours at 550 ℃, and cerium dioxide is prepared.
Example 7 (reference): 1% K/CeO2Preparation of the catalyst
a) 4.28ml of 0.1mol/L potassium nitrate solution is added with deionized water and stirred evenly; taking 2gCeO2(preparation method is same as example 6) is added into the solution and stirred for 6 hours to prepare slurry;
b) drying the slurry prepared in the step a) at 120 ℃ for 12 hours to prepare a dried sample. The sample was calcined in a muffle furnace at 500 ℃ for 4 hours to obtain 1% K/CeO2A catalyst.
Example 8 (reference): 6% Fe2(SO4)3/TiO2Preparation of the catalyst
a) 3.19ml of 0.10mol/L ferric sulfate solution is taken, added with deionized water and stirred uniformly; adding 2g of titanium dioxide into the solution, and stirring for 6 hours to prepare slurry;
b) drying the slurry prepared in the step (a) at 120 ℃ for 16 hours to prepare a dried sample; the sample is placed in a muffle furnace to be roasted for 4 hours at the temperature of 500 ℃ to prepare 6 percent Fe2(SO4)3/TiO2A catalyst.
Example 9 (reference): 1% K/6% Fe2(SO4)3/TiO2Preparation of the catalyst
a) 4.28ml of 0.1mol/L potassium nitrate solution is added with deionized water and stirred evenly; 2g of 6% Fe2(SO4)3/TiO2(preparation method is the same as example 8) is added into the solution, and stirred for 6 hours to prepare slurry;
b) drying the slurry prepared in the step a) at 120 ℃ for 12 hours to prepare a dried sample. The sample was calcined in a muffle furnace at 500 ℃ for 4 hours to yield 1% K/6% Fe2(SO4)3/TiO2A catalyst.
Example 10: the catalyst was prepared in the same manner as in example 1 by placing 0.12g of the catalyst in a continuous flow fixed bed reactor with a reaction gas composition of 500ppm NO and 500ppm NH3，5％O2Nitrogen is used as balance gas, the flow rate of reaction gas is 300ml/min, and the space velocity is 118000h-1. The activity evaluation temperature range is 250-450 ℃, and the catalyst reduces NO at different temperaturesxThe conversion of (D) is shown in Table 1.
Example 11: the catalyst was prepared in the same manner as in example 2, by placing 0.12g of the catalyst in a continuous flow fixed bed reactor with a reaction gas composition of 500ppm NO and 500ppm NH3，5％O2Nitrogen is used as balance gas, the flow rate of reaction gas is 300ml/min, and the space velocity is 118000h-1. The activity evaluation temperature range is 250-450 ℃, and the catalyst reduces NO at different temperaturesxThe conversion of (D) is shown in Table 1.
Example 12: the catalyst was prepared in the same manner as in example 3 by placing 0.12g of the catalyst in a continuous flow fixed bed reactor with a reaction gas composition of 500ppm NO and 500ppm NH3，5％O2Nitrogen is used as balance gas, the flow rate of reaction gas is 300ml/min, and the space velocity is 118000h-1. The activity evaluation temperature range is 250-450 ℃, and the catalyst reduces NO at different temperaturesxThe conversion of (D) is shown in Table 1.
Example 13: the catalyst was prepared in the same manner as in example 4 by placing 0.12g of the catalyst in a continuous flow fixed bed reactor with a reaction gas composition of 500ppm NO and 500ppm NH3，5％O2Nitrogen is used as balance gas, the flow rate of reaction gas is 300ml/min, and the space velocity is 118000h-1. The activity evaluation temperature range is 250-450 ℃, and the catalyst reduces NO at different temperaturesxThe conversion of (D) is shown in Table 1.
TABLE 1 Fe2(SO4)3/CeO2Evaluation results of catalyst Activity
Figure BDA0002433921980000051
Example 14: the catalyst was prepared in the same manner as in example 5 by placing 0.12g of the catalyst in a continuous flow fixed bed reactor with a reaction gas composition of 500ppm NO and 500ppm NH3，5％O2Nitrogen is used as balance gas, the flow rate of reaction gas is 300ml/min, and the space velocity is 118000h-1. The activity evaluation temperature range is 250-450 ℃, and the alkali metal resistance of the catalyst is shown in Table 2 at different temperatures.
TABLE 2 Fe2(SO4)3/CeO2Alkali metal resistance of the catalyst
Figure BDA0002433921980000061

Claims (3)

1. The cerium dioxide loaded ferric sulfate catalyst is characterized in that: the catalyst takes cerium dioxide as a carrier and ferric sulfate as an active component, and the composition of the catalyst is expressed as Fe2(SO4)3/CeO2The mass percentage of ferric sulfate is 2-10%;
the cerium dioxide supported ferric sulfate catalyst is prepared by the following method, and the method comprises the following steps:
(1) preparing 0.05-0.20 mol/L ferric sulfate solution;
(2) roasting cerium nitrate in a muffle furnace at 550 ℃ for 4 hours to prepare cerium dioxide;
(3) adding deionized water into the ferric sulfate solution obtained in the step (1), uniformly stirring at room temperature, adding the cerium dioxide obtained in the step (2) into the solution, and stirring for 4-8 hours to obtain slurry;
(4) drying the slurry prepared in the step (3) at 120 ℃ for 12-24 hours to prepare a dried sample; placing the sample in a muffle furnace to be roasted for 4-8 hours at 500 ℃ to prepare Fe2(SO4)3/CeO2A catalyst.
2. A method of preparing the ceria supported iron sulfate catalyst of claim 1, comprising the steps of:
(1) preparing 0.05-0.20 mol/L ferric sulfate solution;
(2) roasting cerium nitrate in a muffle furnace at 550 ℃ for 4 hours to prepare cerium dioxide;
(3) adding deionized water into the ferric sulfate solution obtained in the step (1), uniformly stirring at room temperature, adding the cerium dioxide obtained in the step (2) into the solution, and stirring for 4-8 hours to obtain slurry;
(4) drying the slurry prepared in the step (3) at 120 ℃ for 12-24 hours to prepare a dried sample; placing the sample in a muffle furnace to be roasted for 4-8 hours at 500 ℃ to prepare Fe2(SO4)3/CeO2A catalyst.
3. The use of the ceria-supported iron sulfate catalyst of claim 1, wherein: NO in fixed source smoke or diesel vehicle tail gasxElimination of (2).
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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN102008967A (en) * 2010-11-01 2011-04-13 清华大学 Ferric sulfate catalyst and preparation method thereof
CN106492812A (en) * 2016-09-14 2017-03-15 昆明理工大学 A kind of meso-pore CexFe1‑xO2The preparation method of solid solution catalyst
CN106824165A (en) * 2017-04-17 2017-06-13 中国科学技术大学 The preparation method of CeO 2 supporting high-dispersion nano catalyst
CN110124680A (en) * 2019-06-24 2019-08-16 江苏浩日朗环保科技有限公司 Using ceria as denitrating catalyst of basis material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102008967A (en) * 2010-11-01 2011-04-13 清华大学 Ferric sulfate catalyst and preparation method thereof
CN106492812A (en) * 2016-09-14 2017-03-15 昆明理工大学 A kind of meso-pore CexFe1‑xO2The preparation method of solid solution catalyst
CN106824165A (en) * 2017-04-17 2017-06-13 中国科学技术大学 The preparation method of CeO 2 supporting high-dispersion nano catalyst
CN110124680A (en) * 2019-06-24 2019-08-16 江苏浩日朗环保科技有限公司 Using ceria as denitrating catalyst of basis material and preparation method thereof

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Promotion of surface acidity and surface species of doped Fe and SO42- over CeO2 catalytic for NH3-SCR reaction;Xuejun Zhang et al.;《Molecular Catalysis》;20181115;第463卷;第1页摘要，第2页第2.1节 *

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