A solid electrolytic reactor for the synergistic removal of NO X and VOCs and method of manufacture

Abstract

The present application relates to a kind of solid electrolyte reactors for synergistically removing NO X And VOCs.The reactor includes a solid electrolyte substrate and a cathode located on one side of the solid electrolyte substrate and an anode located on the other side of the solid electrolyte substrate, and the cathode and the anode are made of the same material. Both the cathode and the anode are porous structures, and both the cathode and the anode contain La 0.5 Pr 1.5‑x Ba x NiO4(LPB x N) and Ce 0.8 Sm 0.2 O 1.9 (SDC), wherein Ce 0.8 Sm 0.2 O 1.9 (SDC) accounts for 30-40% of the total mass. This method does not require the addition of a reducing agent, and can effectively avoid the problems of temperature window mismatch, limited reaction sites, and catalyst poisoning when using the traditional NH3-SCR method to synergistically remove NOx and VOCs. At the same time, VOCs can consume excess O2 in the gas, reducing the competition for reduction between cathode O2 and NO X .

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electrochemical degradation of gaseous pollutants, in particular to a solid electrolyte reactor for synergistically removing NO X and VOCs and a preparation method thereof. BACKGROUND

[0002] Nitrogen oxides (NOx) and volatile organic compounds (VOCs) are two important pollutants in the atmosphere, which can cause serious harm to the ecological environment and public health. In addition, the synergistic control of fine particulate matter (PM 2.5 ) and ozone (O3) has become the key to continuously improving air quality in China, and NOx and VOCs are common precursors of both, so achieving synergistic reduction of NOx and VOCs is the most effective means to achieve synergistic control of PM 2.5 and O3.

[0003] Some research in recent years shows that NH3-SCR based denitration synergistic control of VOCs is considered one of the most efficient and economical technical options, but this method generally has the following technical problems: (1) the temperature window of NOx reduction reaction and VOCs oxidation reaction does not match, and a catalyst with a suitable temperature window needs to be developed; (2) NOx will compete with VOCs for limited reaction sites on a single catalyst, thereby reducing pollutant removal performance; (3) complex flue gas environment can cause catalyst poisoning, and even produce various by-products, thereby causing secondary pollution. SUMMARY

[0004] The purpose of the present application is to provide a solid electrolyte reactor for synergistically removing NO X and VOCs, so as to solve the technical problems of temperature window mismatch, limited reaction sites, and catalyst poisoning when using the traditional NH3-SCR method to synergistically remove NOx and VOCs in the prior art; at the same time, the purpose of the present application is also to provide a preparation method of the above-mentioned solid electrolyte reactor.

[0005] To achieve the above-mentioned purpose, the solid electrolyte reactor for synergistically removing NO X and VOCs of the present application adopts the following technical scheme: a solid electrolyte reactor for synergistically removing NO X and VOCs, comprising a solid electrolyte substrate and a cathode located on one side of the solid electrolyte substrate and an anode located on the other side of the solid electrolyte substrate, the cathode and the anode are made of the same material; the cathode and the anode are both porous structures, and the cathode and the anode both contain La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) and Ce 0.8 Sm 0.2 O1.9 (SDC), wherein Ce 0.8 Sm 0.2 O 1.9 (SDC) is 30-40% of the total mass of both.

[0006] Both the cathode and the anode are made of La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder and Ce 0.8 Sm 0.2 O 1.9 The (SDC) powder is mixed with a binder to make an electrode slurry, and is screen-printed on the corresponding side of the solid electrolyte substrate.

[0007] La 0.5 P r1.5-x Ba x NiO4(LPB x N) powder is prepared by the following method:

[0008] 1) La(NO3)3·6H2O, PrN3O9·6H2O, Ba(NO3)2 and Ni(NO3)2·6H2O are dissolved in distilled water, and the molar ratio of La, Pr, Ba and Ni metal ions is controlled to be 0.5:1.5-x:x:1;

[0009] 2) Citric acid and ethylenediaminetetraacetic acid are added to the above solution, and the molar ratio is controlled to be metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5;

[0010] 3) Water bath heating, and ammonia water is added to the solution of step 2) to adjust the pH to 6-8, and stirring to obtain a wet gel;

[0011] 4) The wet gel in step 3) is dried to obtain a loose and porous dry gel;

[0012] 5) The dry gel is calcined to obtain La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder.

[0013] Ce 0.8 Sm 0.2 O 1.9 The (SDC) powder is prepared by the following method:

[0014] 1) Ce(NO3)3·6H2O and Sm(NO3)3·6H2O are dissolved in distilled water, and the molar ratio of Ce and Sm metal ions is controlled to be 8:2;

[0015] 2) Citric acid and ethylenediaminetetraacetic acid are added to the above solution, and the molar ratio of the total amount of metal ions: ethylenediaminetetraacetic acid: citric acid is controlled to be 1:1:1.5;

[0016] 3) The solution is heated in a water bath, and ammonia water is added to adjust the pH to 6-8, and stirring is performed to obtain a wet gel;

[0017] 4) The wet gel in step 3) is dried to obtain a loose and porous dry gel;

[0018] 5) The dry gel is calcined to obtain Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0019] The solid electrolyte substrate is a yttrium-stabilized zirconia (YSZ) substrate.

[0020] The preparation method of the above-mentioned solid electrolyte reactor of the present application adopts the following technical scheme: a preparation method of the solid electrolyte reactor for simultaneously removing NO X and VOCs according to claim 1, comprising the following steps,

[0021] 1) preparing a solid electrolyte substrate, La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder;

[0022] 2) preparing an electrode slurry from the metal oxide powder in step 1);

[0023] 3) using the electrode slurry in step 2) to make a cathode attached to one side of the solid electrolyte substrate and an anode attached to the other side of the solid electrolyte substrate by screen printing based on the solid electrolyte substrate to obtain a solid electrolyte reactor.

[0024] In step 1), the solid electrolyte substrate is prepared by the following method: taking yttrium-stabilized zirconia (YSZ) powder, dry pressing the electrolyte green body under a pressure of 180-200 Mpa, and then calcining to obtain the solid electrolyte substrate.

[0025] In step 1), the La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder is prepared by the following method:

[0026] 1) La(N03)3-6H20, PrN30g-6H20, Ba(N03)2 and Ni(N03)2-6H20 were dissolved in distilled water, and the molar ratio of La, Pr, Ba and Ni metal ions was controlled to be 0.5:1.5-x:x:1;

[0027] 2) Citric acid and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio was controlled to be total amount of metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5;

[0028] 3) Water bath heating, and ammonia water was added to the solution of step 2) to adjust the pH to 6-8, and stirring to obtain a wet gel;

[0029] 4) The wet gel in step 3) was dried to obtain a loose and porous dry gel;

[0030] 5) The dry gel was calcined to obtain La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder.

[0031] In step 1), Ce 0.8 Sm 0.2 O 1.9 (SDC) powder was prepared by the following method:

[0032] 1) Ce(N03)3-6H20 and Sm(N03)3-6H20 were dissolved in distilled water, and the molar ratio of Ce and Sm metal ions was controlled to be 8:2;

[0033] 2) Citric acid and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio was controlled to be total amount of metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5;

[0034] 3) Water bath heating, and ammonia water was added to the solution to adjust the pH to 6-8, and stirring to obtain a wet gel;

[0035] 4) The wet gel in step 3) was dried to obtain a loose and porous dry gel;

[0036] 5) The dry gel was calcined to obtain Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0037] In step 2), the electrode slurry was prepared by the following method: La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder and Ce 0.8 Sm0.2 O 1.9 (SDC) powder, Ce 0.8 Sm 0.2 O 1.9 (SDC) powder accounts for 30-40% of the total mass of the two, after grinding, adding a binder, the mass ratio of the total amount of metal oxide powder and the binder is 1:1.5, and continuous grinding obtains an electrode slurry.

[0038] The beneficial effects of the present application: the present application constructs a solid electrolyte reactor based on a LPB x N-SDC electrode. The electrode has good porosity and large specific surface area, which can provide sufficient active adsorption sites for catalytic reaction, and barium doping effectively improves the pollutant removal rate and current density of the electrode, and reduces the polarization resistance. LPB x N as an R-P type perovskite powder, its unique AO rock salt layer can accommodate additional interstitial oxygen, and endows the material with high oxygen surface exchange coefficient and bulk diffusion coefficient, and sufficient oxygen ion conductivity. SDC powder has high oxygen ion conductivity and good chemical matching with electrolyte. NO x adsorbed on the cathode and reduced to N2 by obtaining electrons and producing O 2- ions, O 2- ions are transmitted to the anode through the solid electrolyte and react with VOCs adsorbed on the anode to generate CO2 and H2O. This method does not need to add reducing agent, which can effectively avoid the problems of temperature window mismatch, limited reaction sites and catalyst poisoning in the traditional NH3-SCR method for simultaneous removal of NOx and VOCs. At the same time, VOCs can consume excess O2 in the gas, reducing the competition of cathode O2 and NOx for reduction. BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1 is a working principle diagram of a solid electrolyte reactor for simultaneous removal of NO X and VOCs of the present application;

[0040] Figure 2 is a structural diagram of a solid electrolyte reactor for simultaneous removal of NO X and VOCs of the present application;

[0041] Figure 3 is a structural diagram of a NOx and VOCs simultaneous removal reaction device built;

[0042] Figure 4 is the XRD spectrum of the electrode of the LPN-SDC reactor and the LPB 0.1 N-SDC reactor in Example One;

[0043] Figure 5 is the LPB in the LPN-SDC reactor and Example 1 0.1 SEM of the electrode of the N-SDC reactor;

[0044] Figure 6 is the LPB in the LPN-SDC reactor and Example 1 0.1 SEM of the cross section of the N-SDC reactor;

[0045] Figure 7 is the LPB in the LPN-SDC reactor and Example 1 0.1 (a) NO conversion and (b) propane conversion of the N-SDC reactor at 750°C in the presence of 1000 ppm NO and 2000 ppm C3H8;

[0046] Figure 8 is the LPB in the LPN-SDC reactor and Example 1 0.1 (a) NO conversion and (b) propane conversion of the N-SDC reactor at 750°C in the presence of 1000 ppm NO, 2000 ppm C3H8 and 2.0 vol% O2;

[0047] Figure 9 is the LPB in the LPN-SDC reactor and Example 1 0.1 (a) in the presence of 1000 ppm NO and 2000 ppm C3H8 and (b) in the presence of 1000 ppm NO, 2000 ppm C3H8 and 2.0 vol% O2 at 750°C, the N-SDC reactor's impedance spectrogram;

[0048] Figure 10 is the LPB in the LPN-SDC reactor and Example 1 0.1 (a) in the presence of 1000 ppm NO and 2000 ppm C3H8 and (b) in the presence of 1000 ppm NO, 2000 ppm C3H8 and 2.0 vol% O2 at 750°C, the N-SDC reactor's I-V curve;

[0049] BRIEF DESCRIPTION OF DRAWINGS x N; 4, SDC; 5, outer wall of the reaction chamber; 6, corundum tube; 7, gas outlet; 8, gas inlet; 9, solid electrolyte reactor; 10, solid electrolyte substrate; 11, anode; 12, cathode; 13, direct current power supply; 14, silver wire; 15, temperature controller; 16, thermocouple; 17, heating element. DETAILED DESCRIPTION

[0050] A solid electrolyte reactor for synergistically removing NO X and VOCs, such asFigure 1 and 2 As shown, it includes a solid electrolyte substrate 2, a cathode located on one side of the solid electrolyte substrate and an anode 1 located on the other side of the solid electrolyte substrate. The cathode and the anode are made of the same material, both of which are porous structures, and both of which include La 0.5 Pr 1.5- x Ba x NiO4(LPB x N) and Ce 0.8 Sm 0.2 O 1.9 (SDC), where x represents the doping amount of Ba ions, specifically the amount of Ba ions replacing Pr ions, and x is less than or equal to 0.2. For example, x = 0, then the chemical formula is La 0.5 Pr 1.5 NiO4, indicating that there is no Ba ion replacing the Pr position, which is an undoped state; if x = 0.1, the chemical formula is La 0.5 Pr 1.4 Ba 0.1 NiO4 means that in each chemical formula unit, 0.1 mol of Pr is replaced by Ba. 0.5 Pr 1.5-x Ba x NiO4(LPB x N) and Ce 0.8 Sm 0.2 O 1.9 The reference numerals of (SDC) are 3 and 4. The solid electrolyte substrate 2 is a yttria-stabilized zirconia (YSZ) substrate.

[0051] The solid electrolyte reactor of the present invention synergistically removes NO X The principle of VOCs is as follows: Figure 1 As shown, taking NO and propane (C3H8) as an example, NO is adsorbed on the cathode and obtains electrons to be reduced to N2 and produce O 2- ions, O 2- Ions are transferred to the anode through the solid electrolyte and react with C3H8 adsorbed on the anode to generate CO2 and H2O. This method does not require the addition of a reducing agent and can effectively avoid the problems of temperature window mismatch, limited reaction sites, and easy catalyst poisoning when the traditional NH3-SCR method is used to remove NOx and VOCs in a coordinated manner. At the same time, VOCs can consume excess O2 in the flue gas, reducing the cathode O2 and NO x Competitive reduction.

[0052] The preparation method of the solid electrolyte reactor is described in detail below with reference to an embodiment:

[0053] Example 1

[0054] 1) Preparation of solid electrolyte substrate, La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0055] Preparation of solid electrolyte substrate: Take yttrium stabilized zirconia (YSZ) powder 200 mg, dry-press to form electrolyte green body under 200 MPa pressure, then place in muffle furnace to calcine at 1400 °C for 4 h to obtain solid electrolyte substrate with diameter of about 1 cm and thickness of about 330 μm.

[0056] La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder:

[0057] Dissolve La(N03)3-6H20, PrN3O9-6H20, Ba(N03)2 and Ni(N03)2-6H20 in beaker in distilled water, control the molar ratio of La, Pr, Ba and Ni metal ions to be 0.5:1.4:0.1:1. Add citric acid and ethylenediaminetetraacetic acid to the above solution, control the molar ratio to be total amount of metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5. Place the beaker in a water bath at 80 °C and continue to heat, and add ammonia water to the beaker to adjust the pH to 7, continue to stir until the solution becomes a light blue wet gel with viscosity. Transfer the wet gel in the beaker to a porcelain crucible and place it in a forced air drying oven, set the temperature to 160 °C, and continue to dry to obtain a loose and porous dry gel. Place the dry gel in a muffle furnace and calcine at 950 °C for 5 h, and grind to obtain black La 0.5 Pr 1.4 Ba 0.1 NiO4(LPB 0.1 N) powder.

[0058] Preparation of Ce 0.8 Sm 0.2 O 1.9 (SDC) powder:

[0059] Ce(NO3)3-6H2O and Sm(NO3)3-6H2O were dissolved in distilled water in a beaker, and the molar ratio of Ce and Sm metal ions was controlled to be 8:2. Citric acid and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio was controlled to be total amount of metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5. The beaker was placed in a water bath crucible at 80°C for continuous heating, and ammonia water was added to the solution to adjust the pH to 7, and the solution was continuously stirred by a magnetic stirrer until the solution became a wet gel with viscosity. The wet gel in the beaker was transferred to a porcelain crucible and placed in a forced air drying oven, and the temperature was set to 160°C for continuous drying to obtain a loose and porous dry gel. The dry gel was transferred to a muffle furnace and calcined at 900°C for 3h to obtain Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0060] 2) The metal oxide powder in step 1) was used to prepare an electrode slurry.

[0061] La 0.5 Pr 1.4 Ba 0.1 NiO4(LPB 0.1 N) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder were weighed in a mortar, and the mass ratio of Ce 0.8 Sm 0.2 O 1.9 (SDC) was 35%. Then, the mixture was ground for 30 min, and then terpineol was added as a binder, and the mass ratio of the mixture and terpineol was controlled to be 1:1.5, and the grinding was continued until a uniform and slightly sticky electrode slurry was obtained.

[0062] 3) The electrode slurry in step 2) was used to make a cathode attached to one side of a solid electrolyte substrate and an anode attached to the other side of the solid electrolyte substrate by screen printing based on the solid electrolyte substrate to obtain a solid electrolyte reactor.

[0063] Specifically, the prepared electrode slurry was screen printed on one side of the solid electrolyte substrate and dried in an oven at 140°C, and after taking out, the electrode slurry was attached to the other side of the solid electrolyte substrate in the same way, and dried in the oven at 140°C. Finally, the complete solid electrolyte reactor was obtained by calcining in a muffle furnace at 1050°C for 4h.

[0064] Example Two

[0065] 1) A solid electrolyte substrate, La 0.5 Pr 1.5-x Ba xNiO4(LPB x N) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0066] Preparation of solid electrolyte substrate: 200 mg of yttrium stabilized zirconia (YSZ) powder was dry-pressed at a pressure of 180 MPa to form a green electrolyte, which was then calcined in a muffle furnace at 1400 °C for 4 h to obtain a solid electrolyte substrate with a diameter of about 1 cm and a thickness of about 330 μm.

[0067] La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder:

[0068] La(NO3)3-6H2O, PrN3O9-6H2O, Ba(NO3)2and Ni(NO3)2-6H2O were dissolved in distilled water in a beaker, and the molar ratio of La, Pr, Ba and Ni metal ions was controlled to be 0.5:1.4:0.1:1. Citric acid and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio was controlled to be metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5. The beaker was placed in a water bath at 80 °C and heated continuously, and ammonia was added to the beaker to adjust the pH to 6, and stirring was continued until the solution became a light blue wet gel with viscosity. The wet gel in the beaker was transferred to a porcelain crucible and placed in a forced air drying oven, and the temperature was set to 160 °C. The dry gel was calcined in a muffle furnace at 950 °C for 5 h, and then ground to obtain black La 0.5 Pr 1.4 Ba 0.1 NiO4(LPB 0.1 N) powder.

[0069] Ce 0.8 Sm 0.2 O 1.9 (SDC) powder:

[0070] In a beaker, Ce(N03)3*6H20 and Sm(N03)3*6H20 were dissolved in distilled water, and the molar ratio of Ce and Sm metal ions was controlled to be 8:2. Citric acid and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio was controlled to be total amount of metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5. The beaker was placed in a water bath crucible at 80°C for continuous heating, and ammonia water was added to the solution to adjust the pH to 6, and the solution was continuously stirred by a magnetic stirrer until the solution became a wet gel with viscosity. The wet gel in the beaker was transferred to a porcelain crucible and placed in a forced air drying oven, and the temperature was set to 160°C for continuous drying to obtain a loose and porous dry gel. The dry gel was transferred to a muffle furnace and calcined at 900°C for 3h to obtain Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0071] 2) The metal oxide powder in step 1) was used to prepare an electrode slurry.

[0072] La 0.5 Pr 1.4 Ba 0.1 NiO4(LPB 0.1 N) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder in a mortar, that is, Ce 0.8 Sm 0.2 O 1.9 (SDC) accounted for 40% of the mass ratio of the two. Grinding for 30 min, then adding terpineol as a binder, and the mass ratio of the mixed powder to terpineol was controlled to be 1:1.5, and the grinding was continued until a uniform and slightly sticky electrode slurry was obtained.

[0073] 3) The electrode slurry in step 2) was used to make a cathode attached to one side of a solid electrolyte substrate and an anode attached to the other side of the solid electrolyte substrate by screen printing based on the solid electrolyte substrate, to obtain a solid electrolyte reactor.

[0074] Specifically, the prepared electrode slurry was screen printed on one side of the solid electrolyte substrate and dried in an oven at 140°C, and after taking out, the electrode slurry was attached to the other side of the solid electrolyte substrate in the same way, and dried in the oven at 140°C. Finally, calcining in a muffle furnace at 1050°C for 4h, a complete solid electrolyte reactor was obtained.

[0075] Example Three

[0076] 1) A solid electrolyte substrate, La 0.5 Pr 1.5-x Ba xNiO4(LPB x N) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0077] Preparation of solid electrolyte substrate: 200 mg of yttrium stabilized zirconia (YSZ) powder was dry-pressed at 200 MPa to form a green electrolyte compact, which was then calcined in a muffle furnace at 1400 °C for 4 h to obtain a solid electrolyte substrate with a diameter of about 1 cm and a thickness of about 330 μm.

[0078] La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder:

[0079] La(NO3)3-6H2O, PrN3O9-6H2O, Ba(NO3)2and Ni(NO3)2-6H2O were dissolved in distilled water in a beaker, and the molar ratio of La, Pr, Ba and Ni metal ions was controlled to be 0.5:1.4:0.1:1. Citric acid and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio was controlled to be metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5. The beaker was placed in a water bath at 80 °C for continuous heating, and ammonia was added to the beaker to adjust the pH to 8. The solution was continuously stirred until it became a light blue wet gel with viscosity. The wet gel in the beaker was transferred to a porcelain crucible and placed in a forced air drying oven, which was set to a temperature of 160 °C. The porous dry gel was obtained by continuous drying. The dry gel was calcined in a muffle furnace at 950 °C for 5 h, and then ground to obtain black La 0.5 Pr 1.4 Ba 0.1 NiO4(LPB 0.1 N) powder.

[0080] Ce 0.8 Sm 0.2 O 1.9 (SDC) powder:

[0081] In a beaker, Ce(N03)3*6H20 and Sm(N03)3*6H20 were dissolved in distilled water, and the molar ratio of Ce and Sm metal ions was controlled to be 8:2. Citric acid and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio was controlled to be total amount of metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5. The beaker was placed in a water bath crucible at 80°C for continuous heating, and ammonia water was added to the solution to adjust the pH to 8, and the solution was continuously stirred by a magnetic stirrer until the solution became a wet gel with viscosity. The wet gel in the beaker was transferred to a porcelain crucible and placed in a forced air drying oven, and the temperature was set to 160°C for continuous drying to obtain a loose and porous dry gel. The dry gel was transferred to a muffle furnace and calcined at 900°C for 3h to obtain a Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0082] 2) The metal oxide powder in step 1) was used to prepare an electrode slurry.

[0083] La 0.5 Pr 1.4 Ba 0.1 NiO4(LPB 0.1 N) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder were weighed in a mortar, and the mass ratio of Ce 0.8 Sm 0.2 O 1.9 (SDC) was 30%. The mixture was ground for 30 min, and then terpineol was added as a binder, and the mass ratio of the mixture and terpineol was controlled to be 1:1.5, and the mixture was continuously ground until a uniform and slightly sticky electrode slurry was obtained.

[0084] 3) The electrode slurry in step 2) was used to make a cathode attached to one side of a solid electrolyte substrate and an anode attached to the other side of the solid electrolyte substrate by screen printing based on the solid electrolyte substrate, to obtain a solid electrolyte reactor.

[0085] Specifically, the prepared electrode slurry was screen printed on one side of the solid electrolyte substrate and dried in an oven at 140°C, and after taking out, the electrode slurry was attached to the other side of the solid electrolyte substrate in the same way, and dried in the oven at 140°C. Finally, the complete solid electrolyte reactor was obtained by calcining in a muffle furnace at 1050°C for 4h.

[0086] Example Four

[0087] 1) A solid electrolyte substrate, La 0.5 Pr 1.5-x Ba xNiO4(LPB x N) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0088] Preparation of solid electrolyte substrate: 200 mg of yttrium stabilized zirconia (YSZ) powder was dry-pressed at 200 MPa to form a green electrolyte, which was then calcined in a muffle furnace at 1400 °C for 4 h to obtain a solid electrolyte substrate with a diameter of about 1 cm and a thickness of about 330 μm.

[0089] La 0.5 Pr 1.5-x Ba x NiO4(LPB x N) powder:

[0090] La(NO3)3-6H2O, PrN3O9-6H2O, Ba(NO3)2and Ni(NO3)2-6H2O were dissolved in distilled water in a beaker, and the molar ratio of La, Pr, Ba and Ni metal ions was controlled to be 0.5:1.3:0.2:1. Citric acid and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio was controlled to be metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5. The beaker was placed in a water bath at 80 °C and heated continuously, and ammonia was added to the beaker to adjust the pH to 7, and stirring was continued until the solution became a light blue wet gel with viscosity. The wet gel in the beaker was transferred to a porcelain crucible and placed in a forced air drying oven, and the temperature was set to 160 °C. The dry gel was calcined at 950 °C for 5 h in a muffle furnace, and the black La 0.5 Pr 1.3 Ba 0.2 NiO4(LPB 0.2 N) powder.

[0091] Ce 0.8 Sm 0.2 O 1.9 Preparation of Ce

[0092] Ce(NO3)3-6H2O and Sm(NO3)3-6H2O were dissolved in distilled water in a beaker, and the molar ratio of Ce and Sm metal ions was controlled to be 8:2. Citric acid and ethylenediaminetetraacetic acid were added to the above solution, and the molar ratio was controlled to be total amount of metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1.5. The beaker was placed in a water bath crucible at 80°C for continuous heating, and ammonia water was added to the solution to adjust the pH to 7, and the solution was continuously stirred by a magnetic stirrer until the solution became a wet gel with viscosity. The wet gel in the beaker was transferred to a porcelain crucible and placed in a forced air drying oven, and the temperature was set to 160°C for continuous drying to obtain a loose and porous dry gel. The dry gel was transferred to a muffle furnace and calcined at 900°C for 3h to obtain a Ce 0.8 Sm 0.2 O 1.9 (SDC) powder.

[0093] 2) The metal oxide powder in step 1) was used to prepare an electrode slurry.

[0094] La 0.5 Pr 1.3 Ba 0.2 NiO4(LPB 0.2 N) powder and Ce 0.8 Sm 0.2 O 1.9 (SDC) powder were weighed in a mortar, that is, Ce 0.8 Sm 0.2 O 1.9 (SDC) accounted for 35% of the mass ratio of the two. Then grinding for 30 min, followed by the addition of terpineol as a binder, and the mass ratio of the mixed powder to terpineol was controlled to be 1:1.5, and the grinding was continued until a uniform and slightly sticky electrode slurry was obtained.

[0095] 3) The electrode slurry in step 2) was used to make a cathode attached to one side of a solid electrolyte substrate and an anode attached to the other side of the solid electrolyte substrate by screen printing based on the solid electrolyte substrate, to obtain a solid electrolyte reactor.

[0096] Specifically, the prepared electrode slurry was screen printed on one side of the solid electrolyte substrate and dried in an oven at 140°C, and after taking out, the electrode slurry was attached to the other side of the solid electrolyte substrate in the same way, and dried in the oven at 140°C. Finally, calcining in a muffle furnace at 1050°C for 4h, a complete solid electrolyte reactor was obtained.

[0097] Comparative Example

[0098] The molar ratio of La:Pr:Ba:Ni metal ions in the experimental example one is modified to 0.5:1.5:0:1, that is, without barium doping, and the rest of the conditions are the same as in example one, and the obtained solid electrolyte reactor is recorded as LPB

[0099] In order to verify the effect of the present application, the following tests are carried out on the product of example one (LPB 0.1 N-SDC reactor) and the product of the comparative example (LPN-SDC reactor), wherein: the XRD spectrum of the electrode of the LPN-SDC reactor is as shown in 0.1 Figure 1. The XRD spectrum of the electrode of the LPB x N-SDC reactor is as shown in Figure 2. The prepared LPB 0.1 N powder shows a single R-P single phase without impurity peaks, and the barium doping makes the material change from an orthorhombic system to a tetragonal system, increasing the symmetry of the crystal structure. The scanning electron microscope image of the electrode of the LPN-SDC reactor and the electrode of the LPB 0.1 N-SDC reactor is as shown in Figure 5 Figure 3. The electrode shows a porous structure, which is beneficial to the adsorption and diffusion process of the gas on the electrode. The cross-sectional scanning electron microscope image of the LPB x N-SDC reactor is as shown in Figure 6 Figure 4. The electrode presents a loose and porous structure, while the electrolyte presents a dense structure, and the thicknesses thereof are about 7.4 μm and 333 μm, respectively.

[0100] The NO 0.1 and VOCs cooperative removal reaction device is built: the gas reaction device includes a reaction chamber outer wall 5, a corundum pipe 6 is arranged in the reaction chamber outer wall, the inner cavity of the corundum pipe forms a gas reaction chamber, and the gas reaction chamber has a gas inlet 8 and a gas outlet 7. The gas reaction device further includes a direct current power supply 13 and a heating device. The solid electrolyte reactor 9 is vertically arranged in the gas reaction chamber, and the cathode and the anode are connected with the direct current power supply 13 through conductive silver paste and a silver wire 14. The heating device provides the required temperature for the gas reaction chamber, and the temperature is controlled through a temperature controller 15, and a heating rod 17 arranged in the corundum pipe 6 is specifically adopted. A thermocouple 16 is arranged in the gas reaction chamber, and the thermocouple 16 and the heating element 17 are connected with the temperature controller 15, so that the temperature in the gas reaction chamber can be adjusted in real time. Taking NO and C3H8 gas as an example, the performance test is carried out on the LPN-SDC reactor and the LPB 0.1 N-SDC reactor. Specifically as follows:

[0101] 1000ppm NO and 2000ppm C3H8 gas were introduced into the reaction chamber, and the total gas flow rate was controlled at 50mL / min. The temperature was raised to 750℃ at a rate of 5℃ / min by a temperature controller. Then a certain voltage was applied to both ends of the battery through a DC power supply. The inlet and outlet gas concentrations of the reaction chamber were tested using a flue gas analyzer (AW-T6). The test results are as follows: Figure 7 As shown, at 0.8V, LPB 0.1 The NO conversion rate of the N-SDC reactor reached 89.5%, which was higher than the 87.1% of the LPN-SDC reactor. 0.1 The propane conversion of the N-SDC reactor was 77.9%, slightly higher than 77.0% for the LPN-SDC reactor.

[0102] Electrochemical performance test: The electrochemical performance of the electrode was tested using an electrochemical workstation (CHI660E), including electrochemical impedance spectroscopy and IV curves.

[0103] Electrochemical impedance spectroscopy results ( Figure 9 a) shows that the polarization resistance of the LPN-SDC reactor at 750°C is 139.9Ωcm 2 , and the Ba-doped LPB 0.1 The polarization resistance of the N-SDC reactor is 102.4 Ωcm 2 , the polarization resistance is significantly lower than that of undoped ones.

[0104] IV curve results ( Figure 10 a) shows that the current densities of the LPN-SDC reactor at 750 °C at 1.0, 1.5, and 2.0 V are 13.9, 62.9, and 113.2 mA cm, respectively. -2 , and the Ba-doped LPB 0.1 The current densities of the N-SDC reactor at the corresponding voltages were 14.0, 72.1, and 134.7 mA cm -2 .

[0105] Performance test of solid electrolyte reactor in oxygen-containing atmosphere

[0106] The ventilation in the reaction chamber was changed to 1000 ppm NO, 2000 ppm C3H8 and 2.0 vol% O2 gas.

[0107] like Figure 8 As shown, at 2.0V, LPB 0.1 The NO conversion rate of the N-SDC reactor reached 49.9%, which was higher than the 46.0% of the LPN-SDC reactor. 0.1The propane conversion of the N-SDC reactor was 96.2%, slightly higher than the 94.8% of the LPN-SDC reactor.

[0108] Electrochemical impedance spectroscopy results Figure 9 b) indicated that the polarization resistance of the LPN-SDC reactor at 750°C was 4.8 Ω cm 2 while the product of Example One with Ba doping had a polarization resistance of 3.3 Ω cm 2 , a decrease from the undoped value.

[0109] I-V curve results Figure 10 b) indicated that the current density of the LPN-SDC reactor at 750°C at 1.0 and 1.5 V was 106.7 and 148.2 mA cm -2 , respectively, while the LPB 0.1 N-SDC reactor had a current density at the corresponding voltages of 106.6 and 148.6 mA cm -2 , respectively.

Claims

1. A synergistic removal of NO X and VOCs solid electrolyte reactor, characterized by: It includes a solid electrolyte substrate, a cathode located on one side of the solid electrolyte substrate and an anode located on the other side of the solid electrolyte substrate, the cathode and the anode are made of the same material; both the cathode and the anode are porous structures, and both the cathode and the anode contain La 0.5 Pr 1.5-x Ba x NiO4 and Ce0.8Sm0.2O1.9, of which Ce0.8Sm0.2O1.9 accounts for 30%-40% of the total mass of the two.

2. The synergistic removal of NO according to claim 1 X and VOCs solid electrolyte reactor, characterized by: The cathode and anode are both made of La 0.5 Pr 1.5-x Ba x NiO4 powder and Ce0.8Sm0.2O1.9 powder are prepared into electrode slurry with a binder, and the slurry is then formed on the corresponding side surfaces of the solid electrolyte substrate by screen printing.

3. The synergistic removal of NO according to claim 2 X and VOCs solid electrolyte reactor, characterized by: La 0.5 P r1.5-x Ba x NiO4 powder was prepared by the following method: 1) Dissolve La(NO3)3·6H2O, PrN3O9·6H2O, Ba(NO3)2, and Ni(NO3)2·6H2O in distilled water, and control the molar ratio of La, Pr, Ba, and Ni metal ions to be 0.5:1.5-x:x:1; 2) Add citric acid and EDTA to the above solution, controlling the molar ratio of total metal ion: EDTA: citric acid to be 1:1:1.5; 3) heating in a water bath, adding aqueous ammonia to the solution of step 2) to adjust the pH to 6-8, and stirring to obtain a wet gel; 4) drying the wet gel in step 3) to obtain a loose and porous xerogel; 5) Calcinate the dry gel to obtain La 0.5 Pr 1.5-x Ba x NiO4 powder.

4. The synergistic removal of NO according to claim 2 X and VOCs solid electrolyte reactor, characterized by: Ce0.8Sm0.2O1.9 powder was prepared by the following method: 1) Dissolve Ce(NO3)3·6H2O and Sm(NO3)3·6H2O in distilled water, controlling the molar ratio of Ce and Sm metal ions to be 8:2; 2) Add citric acid and EDTA to the above solution, controlling the molar ratio of total metal ion: EDTA: citric acid to be 1:1:1.5; 3) heating in a water bath, adding ammonia water to the solution to adjust the pH to 6-8, and stirring to obtain a wet gel; 4) drying the wet gel in step 3) to obtain a loose and porous xerogel; 5) Calcinate the dry gel to obtain Ce0.8Sm0.2O1.9 powder.

5. The synergistic removal of NO according to claim 1 X and VOCs solid electrolyte reactor, characterized by: The solid electrolyte substrate adopts a yttrium-stabilized zirconia substrate.

6. A synergistic removal of NO as claimed in claim 1 X A method for preparing a solid electrolyte reactor for removing VOCs and volatile organic compounds (VOCs) is characterized by: The following steps are included: 1) Preparation of solid electrolyte substrate, La 0.5 Pr 1.5-x Ba x NiO4 powder and Ce0.8Sm0.2O1.9 powder; 2) preparing an electrode slurry from the metal oxide powder in step 1); 3) The electrode slurry in step 2) is screen-printed on the solid electrolyte substrate to form a cathode attached to one side of the solid electrolyte substrate and an anode attached to the other side, thereby obtaining a solid electrolyte reactor.

7. The synergistic removal of NO according to claim 6 X A method for preparing a solid electrolyte reactor for removing VOCs and volatile organic compounds (VOCs) is characterized by: In step 1), the solid electrolyte substrate is prepared by the following method: yttrium-stabilized zirconia powder is dry-pressed at a pressure of 180-200 MPa to form an electrolyte green body, and then calcined to obtain a solid electrolyte substrate.

8. The synergistic removal of NO according to claim 6 X A method for preparing a solid electrolyte reactor for removing VOCs and volatile organic compounds (VOCs) is characterized by: In step 1), La 0.5 Pr 1.5-x Ba x NiO4 powder was prepared by the following method: 1) Dissolve La(NO3)3·6H2O, PrN3O9·6H2O, Ba(NO3)2, and Ni(NO3)2·6H2O in distilled water, and control the molar ratio of La, Pr, Ba, and Ni metal ions to be 0.5:1.5-x:x:1; 2) Add citric acid and EDTA to the above solution, controlling the molar ratio of total metal ion: EDTA: citric acid to be 1:1:1.5; 3) heating in a water bath, adding aqueous ammonia to the solution of step 2) to adjust the pH to 6-8, and stirring to obtain a wet gel; 4) drying the wet gel in step 3) to obtain a loose and porous xerogel; 5) Calcinate the dry gel to obtain La 0.5 Pr 1.5-x Ba x NiO4 powder.

9. The synergistic removal of NO according to claim 6 X A method for preparing a solid electrolyte reactor for removing VOCs and volatile organic compounds (VOCs) is characterized by: In step 1), Ce0.8Sm0.2O1.9 powder was prepared by the following method: 1) Dissolve Ce(NO3)3·6H2O and Sm(NO3)3·6H2O in distilled water, controlling the molar ratio of Ce and Sm metal ions to be 8:2; 2) Add citric acid and EDTA to the above solution, controlling the molar ratio of total metal ion: EDTA: citric acid to be 1:1:1.5; 3) heating in a water bath, adding ammonia water to the solution to adjust the pH to 6-8, and stirring to obtain a wet gel; 4) drying the wet gel in step 3) to obtain a loose and porous xerogel; 5) Calcinate the dry gel to obtain Ce0.8Sm0.2O1.9 powder.

10. The synergistic removal of NO according to claim 6 X A method for preparing a solid electrolyte reactor for removing VOCs and volatile organic compounds (VOCs) is characterized by: In step 2), the electrode slurry is prepared by the following method: taking La 0.5 Pr 1.5-x Ba x NiO4 powder and Ce0.8Sm0.2O1.9 powder, Ce0.8Sm0.2O1.9 powder accounts for 30-40% of the total mass of the two, and a binder is added after grinding; the mass ratio of the total amount of metal oxide powder to the binder is 1:1.5, and continuous grinding is performed to obtain an electrode slurry.

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