CN106378152A - Supported ceramic catalyst for acrylonitrile removal through supercritical water oxidation - Google Patents
Supported ceramic catalyst for acrylonitrile removal through supercritical water oxidation Download PDFInfo
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- 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
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- C02F1/722—Oxidation by peroxides
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a supported ceramic catalyst for acrylonitrile removal through supercritical water oxidation. The catalyst is prepared through the following steps: cleaning ceramic, and modifying with AgNO3 to prepare a substance M; modifying the substance M with a mixed solution prepared from polyvinylpyrrolidone, methanol, palladium dichloride, ruthenium trichloride trihydrate, concentrated hydrochloric acid and sodium borohydride to prepare a substance N; modifying the substance N with a mixed solution prepared from PbCl2, NiCl2, concentrated nitric acid, urea and ammonium fluoride to prepare a substance O; modifying the substance O with a mixed solution prepared from tetrabutyl titanate, tetraethyl orthosilicate and acetylacetonate to prepare a substance P; modifying the substance P with a mixed solution prepared from NbCl4, MnCl2 and CeCl3 to prepare a substance Q; and modifying the substance Q with a mixed solution prepared from CuCl2, AlCl3, NaOH, Na2CO3 and ZnCl2 to obtain a substance which is the supported ceramic catalyst for acrylonitrile removal through supercritical water oxidation.
Description
Technical field
The invention belongs to the supercritical Water Oxidation Technology field that organic wastewater with difficult degradation thereby is processed, it is used for surpassing particularly to one kind
The support type ceramic catalyst of critical oxidation removal acrylonitrile.
Background technology
Supercritical water oxidation is a kind of wastewater processing technology that the eighties in 20th century grows up, mainly utilize molecular oxygen or
Hydrogen peroxide as oxidant, using supercritical water as solvent, oxidation Decomposition organic pollution.Due to supercritical in oxidizing process
The good dissolubility to various Organic substances and oxygen for the water, Organic substance, oxidant and supercritical water form homogeneous phase, and reaction is not
Meeting restriction hindered because of alternate mass transfer, reaction rate can greatly improve.Supercritical water oxidation treatment technology anti-
Answer generally 400～600 DEG C of temperature, pressure is 30～50MPa, the organic carbon in organic pollution changes into carbon dioxide, hydrogen
Change into water, halogen atom changes into the ion of halogenide, sulfur and phosphorus change into sulfate and phosphate, organic nitrogen transformation respectively
Become nitrogen, these products are nontoxic product.Therefore, supercritical Water Oxidation Technology has clearance height, reacts thorough, place
Effect is good for reason, non-secondary pollution the advantages of.
Although supercritical Water Oxidation Technology is an emerging pollutant treatment technology with broad prospect of application, it is high
The harsh reaction condition of warm high pressure is very high with the requirement of management level to running.Therefore, in order to accelerate reaction rate, reduce instead
Between seasonable, reduce reaction temperature, enable supercritical Water Oxidation Technology to give full play of the advantage of itself, many researcheres will be catalyzed
Agent introduces supercritical Water Oxidation Technology, develops catalytic supercritical water oxidation technology.Conventional in catalytic supercritical water oxidation technology
Catalyst be MnO2、CuO、TiO2、CeO2、Al2O3, the composite catalyst such as Cr of Pt or wherein several material composition2O3/
Al2O3、CuO/A12O3、MnO2/CeO2Deng, but these catalyst existence and stabilities can poor, the shortcomings of catalysis activity is relatively low,
Limit popularization and application in water process for the catalytic supercritical water oxidation technology and development, thus the research of new catalytic material with
Preparation also needs to strengthen further, particularly also lacks the catalyst removing acrylonitrile for supercritical water oxidation at present.
Content of the invention
It is an object of the invention to provide a kind of support type ceramic catalyst removing acrylonitrile for supercritical water oxidation, its
The comprising the following steps that of preparation method：
(1) put into leaching in 500mL acetone after the 149g ceramic particle 300mL deionized water wash being 4～6mm by particle diameter
Bubble 1h, removes liquid and obtains material M0, material M0 obtains material M1 after 300mL deionized water wash, by material M1 after filtration
Put in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L and soak 0.5h, remove liquid after filtration and obtain material M2, thing
In 85 DEG C of drying after matter M2 300mL deionized water wash, then the washing with alcohol being 95% with 500mL mass percent concentration
Place 1.5h in case, obtain material M3, material M3 is added to the AgNO that 250mL molar concentration is 4.33mol/L3In solution,
Temperature be 65 DEG C shaking table in shake 75 minutes, be filtered to remove liquid after being cooled to room temperature and obtain material M4, material M4 warp
100mL mass percent concentration be 97% washing with alcohol after in 76 DEG C of drying baker place 140 minutes, be subsequently placed in Muffle
In stove under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 5.66 grams of Polyvinylpyrrolidone and methanol solution that 650mL mass percent concentration is 80% are added to
Volume is in 1000mL conical flask, stirs 10 minutes, be divided into 5 parts of equivalent, obtain mixed liquor after shaking up under the conditions of 1000r/min
A1, mixed liquor A 2, mixed liquor A 3, mixed liquor A 4, mixed liquor A 5；
(3) 0.8563 gram of palladium chloride and 200mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 in temperature
DEG C water-bath in shake 20 minutes, then place 140 minutes in 120 DEG C of drying baker, be cooled to after room temperature and add 200mL
Deionized water, under the conditions of 1000r/min stir 3 minutes, be divided into 5 parts of equivalent after shaking up, obtain mixed liquid B 1, mixed liquid B 2,
Mixed liquid B 3, mixed liquid B 4, mixed liquid B 5；
(4) 3.27 gram of three hydrate ruthenium trichloride and 850mL deionized water being added to volume is in 1000mL conical flask,
Under the conditions of 1000r/min stir 3 minutes, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor A B1, mixed liquor A B2, mixed liquor A B3,
Mixed liquor A B4, mixed liquor A B5；
(5) sodium borohydride solution being 0.69mol/L by mixed liquor A 1, mixed liquor A B1 and 15mL molar concentration is added to
In mixed liquid B 1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(6) material M is added in mixed liquor C1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material N1, material N1 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N2；
(7) sodium borohydride solution being 0.64mol/L by mixed liquor A 2, mixed liquor A B2 and 13mL molar concentration is added to
In mixed liquid B 2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(8) material N2 is added in mixed liquor C2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material N3, material N3 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N4；
(9) sodium borohydride solution being 0.59mol/L by mixed liquor A 3, mixed liquor A B3 and 11mL molar concentration is added to
In mixed liquid B 3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(10) material N4 is added in mixed liquor C3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material N5, material N5 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N6；
(11) sodium borohydride solution being 0.54mol/L by mixed liquor A 4, mixed liquor A B4 and 9mL molar concentration is added to
In mixed liquid B 4, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C4；
(12) material N6 is added in mixed liquor C4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material N7, material N7 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N8；
(13) sodium borohydride solution being 0.49mol/L by mixed liquor A 5, mixed liquor A B5 and 7mL molar concentration is added to
In mixed liquid B 5, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C5；
(14) material N8 is added in mixed liquor C5, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material N9, material N9 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N；
(15) by 6.33 grams of PbCl2With 8.88 grams of NiCl2It is added in 850mL ethanol, stir 3 under the conditions of 1000r/min
Minute, add 5mL concentrated nitric acid, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4,
Mixed liquor D5；
(16) 3.94 grams of carbamide and 0.59 gram of ammonium fluoride are added in mixed liquor D1, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E1；
(17) material N is added in mixed liquor E1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material O1, material O1 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O2；
(18) 3.84 grams of carbamide and 0.57 gram of ammonium fluoride are added in mixed liquor D2, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E2；
(19) material O2 is added in mixed liquor E2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O3, material O3 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O4；
(20) 3.74 grams of carbamide and 0.55 gram of ammonium fluoride are added in mixed liquor D3, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E3；
(21) material O4 is added in mixed liquor E3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O5, material O5 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O6；
(22) 3.64 grams of carbamide and 0.53 gram of ammonium fluoride are added in mixed liquor D4, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E4；
(23) material O6 is added in mixed liquor E4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O7, material O7 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O8；
(24) 3.54 grams of carbamide and 0.51 gram of ammonium fluoride are added in mixed liquor D5, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E5；
(25) material O8 is added in mixed liquor E5, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O9, material O9 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O；
(26) by positive for 5.37 grams of metatitanic acids four fourth fat being added in 800mL dehydrated alcohol under 1000r/min stirring condition,
Under the conditions of 1000r/min stir 5 minutes, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into 4 parts of equivalent, obtain mixed liquor F1,
Mixed liquor F2, mixed liquor F3, mixed liquor F4；
(27) 2.6mL tetraethyl orthosilicate and 13mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G1；
(28) material O is added in mixed liquor G1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain Substance P 1, Substance P 1 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P 2；
(29) 2.8mL tetraethyl orthosilicate and 15mL acetylacetone,2,4-pentanedione are added in mixed liquor F2, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G2；
(30) Substance P 2 is added in mixed liquor G2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains Substance P 3, Substance P 3 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P 4；
(31) 3.0mL tetraethyl orthosilicate and 17mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G3；
(32) Substance P 4 is added in mixed liquor G3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains Substance P 5, Substance P 5 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P 6；
(33) 3.2mL tetraethyl orthosilicate and 19mL acetylacetone,2,4-pentanedione are added in mixed liquor F4, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G4；
(34) Substance P 6 is added in mixed liquor G4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains Substance P 7, Substance P 7 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P；
(35) by 7.35 grams of NbCl4It is added to volume with the sodium citrate solution that 800mL mass percent concentration is 10%
For, in 1000mL conical flask, stirring 3 minutes under the conditions of 1000r/min, being divided into 4 parts of equivalent after shaking up, obtain mixed liquor H1, mix
Close liquid H2, mixed liquor H3, mixed liquor H4；
(36) MnCl for 0.36mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.75mol/L's
CeCl3Solution is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(37) Substance P is added in mixed liquor J1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material Q1, material Q1 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q2；
(38) MnCl for 0.56mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.55mol/L's
CeCl3Solution is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(39) material Q2 is added in mixed liquor J2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q3, material Q3 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q4；
(40) MnCl for 0.76mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.35mol/L's
CeCl3Solution is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(41) material Q4 is added in mixed liquor J3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q5, material Q5 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q6；
(42) MnCl for 0.96mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.15mol/L's
CeCl3Solution is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(43) material Q6 is added in mixed liquor J4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q7, material Q7 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q；
(44) by 32.07 grams of CuCl2With 12.39 grams of AlCl3It is added in 800mL deionized water, in 1000r/min condition
Lower stirring 10 minutes, is divided into 5 parts of equivalent, obtains mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4, mixed liquor after shaking up
K5；
(45) by 14.04 grams of NaOH and 11.22 gram of Na2CO3It is added in 800mL deionized water, in 1000r/min condition
Lower stirring 10 minutes, is divided into 5 parts of equivalent, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4, mixed liquor after shaking up
L5；
(46) under 1000r/min stirring condition, mixed liquor L1 is added drop-wise in mixed liquor K1, obtains mixed liquor X1, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X1～
10.0, obtain mixed liquor Y1；
(47) ZnCl for 0.27mol/L by 40mL molar concentration2Solution is added in mixed liquor Y1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z1；
(48) material Q is added in mixed liquor Z1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material R1, material R1 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R2；
(49) under 1000r/min stirring condition, mixed liquor L2 is added drop-wise in mixed liquor K2, obtains mixed liquor X2, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X2～
10.0, obtain mixed liquor Y2；
(50) ZnCl for 0.47mol/L by 50mL molar concentration2Solution is added in mixed liquor Y2, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z2；
(51) material R2 is added in mixed liquor Z2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R3, material R3 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R4；
(52) under 1000r/min stirring condition, mixed liquor L3 is added drop-wise in mixed liquor K3, obtains mixed liquor X3, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X3～
10.0, obtain mixed liquor Y3；
(53) ZnCl for 0.67mol/L by 60mL molar concentration2Solution is added in mixed liquor Y3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z3；
(54) material R4 is added in mixed liquor Z3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R5, material R5 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R6；
(55) under 1000r/min stirring condition, mixed liquor L4 is added drop-wise in mixed liquor K4, obtains mixed liquor X4, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X4～
10.0, obtain mixed liquor Y4；
(56) ZnCl for 0.87mol/L by 70mL molar concentration2Solution is added in mixed liquor Y4, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z4；
(57) material R6 is added in mixed liquor Z4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R7, material R7 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R8；
(58) under 1000r/min stirring condition, mixed liquor L5 is added drop-wise in mixed liquor K5, obtains mixed liquor X5, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X5～
10.0, obtain mixed liquor Y5；
(59) ZnCl for 1.07mol/L by 80mL molar concentration2Solution is added in mixed liquor Y5, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z5；
(60) material R8 is added in mixed liquor Z5, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R9, material R9 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, the material obtaining is
It is the support type ceramic catalyst removing acrylonitrile for supercritical water oxidation.
The invention has the beneficial effects as follows, the prepared support type ceramic catalyst removing acrylonitrile for supercritical water oxidation
Have that stability is strong, active height, life-span length, high to acrylonitrile removal efficiency the features such as.
Specific embodiment
The present invention provides a kind of support type ceramic catalyst removing acrylonitrile for supercritical water oxidation, below by one
Individual example is illustrating in fact to apply process.
Embodiment 1.
(1) put into leaching in 500mL acetone after the 149g ceramic particle 300mL deionized water wash being 4～6mm by particle diameter
Bubble 1h, removes liquid and obtains material M0, material M0 obtains material M1 after 300mL deionized water wash, by material M1 after filtration
Put in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L and soak 0.5h, remove liquid after filtration and obtain material M2, thing
In 85 DEG C of drying after matter M2 300mL deionized water wash, then the washing with alcohol being 95% with 500mL mass percent concentration
Place 1.5h in case, obtain material M3, material M3 is added to the AgNO that 250mL molar concentration is 4.33mol/L3In solution,
Temperature be 65 DEG C shaking table in shake 75 minutes, be filtered to remove liquid after being cooled to room temperature and obtain material M4, material M4 warp
100mL mass percent concentration be 97% washing with alcohol after in 76 DEG C of drying baker place 140 minutes, be subsequently placed in Muffle
In stove under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 5.66 grams of Polyvinylpyrrolidone and methanol solution that 650mL mass percent concentration is 80% are added to
Volume is in 1000mL conical flask, stirs 10 minutes, be divided into 5 parts of equivalent, obtain mixed liquor after shaking up under the conditions of 1000r/min
A1, mixed liquor A 2, mixed liquor A 3, mixed liquor A 4, mixed liquor A 5；
(3) 0.8563 gram of palladium chloride and 200mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 in temperature
DEG C water-bath in shake 20 minutes, then place 140 minutes in 120 DEG C of drying baker, be cooled to after room temperature and add 200mL
Deionized water, under the conditions of 1000r/min stir 3 minutes, be divided into 5 parts of equivalent after shaking up, obtain mixed liquid B 1, mixed liquid B 2,
Mixed liquid B 3, mixed liquid B 4, mixed liquid B 5；
(4) 3.27 gram of three hydrate ruthenium trichloride and 850mL deionized water being added to volume is in 1000mL conical flask,
Under the conditions of 1000r/min stir 3 minutes, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor A B1, mixed liquor A B2, mixed liquor A B3,
Mixed liquor A B4, mixed liquor A B5；
(5) sodium borohydride solution being 0.69mol/L by mixed liquor A 1, mixed liquor A B1 and 15mL molar concentration is added to
In mixed liquid B 1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(6) material M is added in mixed liquor C1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material N1, material N1 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N2；
(7) sodium borohydride solution being 0.64mol/L by mixed liquor A 2, mixed liquor A B2 and 13mL molar concentration is added to
In mixed liquid B 2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(8) material N2 is added in mixed liquor C2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material N3, material N3 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N4；
(9) sodium borohydride solution being 0.59mol/L by mixed liquor A 3, mixed liquor A B3 and 11mL molar concentration is added to
In mixed liquid B 3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(10) material N4 is added in mixed liquor C3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material N5, material N5 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N6；
(11) sodium borohydride solution being 0.54mol/L by mixed liquor A 4, mixed liquor A B4 and 9mL molar concentration is added to
In mixed liquid B 4, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C4；
(12) material N6 is added in mixed liquor C4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material N7, material N7 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N8；
(13) sodium borohydride solution being 0.49mol/L by mixed liquor A 5, mixed liquor A B5 and 7mL molar concentration is added to
In mixed liquid B 5, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C5；
(14) material N8 is added in mixed liquor C5, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material N9, material N9 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N；
(15) by 6.33 grams of PbCl2With 8.88 grams of NiCl2It is added in 850mL ethanol, stir 3 under the conditions of 1000r/min
Minute, add 5mL concentrated nitric acid, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4,
Mixed liquor D5；
(16) 3.94 grams of carbamide and 0.59 gram of ammonium fluoride are added in mixed liquor D1, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E1；
(17) material N is added in mixed liquor E1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material O1, material O1 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O2；
(18) 3.84 grams of carbamide and 0.57 gram of ammonium fluoride are added in mixed liquor D2, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E2；
(19) material O2 is added in mixed liquor E2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O3, material O3 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O4；
(20) 3.74 grams of carbamide and 0.55 gram of ammonium fluoride are added in mixed liquor D3, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E3；
(21) material O4 is added in mixed liquor E3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O5, material O5 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O6；
(22) 3.64 grams of carbamide and 0.53 gram of ammonium fluoride are added in mixed liquor D4, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E4；
(23) material O6 is added in mixed liquor E4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O7, material O7 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O8；
(24) 3.54 grams of carbamide and 0.51 gram of ammonium fluoride are added in mixed liquor D5, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E5；
(25) material O8 is added in mixed liquor E5, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O9, material O9 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O；
(26) by positive for 5.37 grams of metatitanic acids four fourth fat being added in 800mL dehydrated alcohol under 1000r/min stirring condition,
Under the conditions of 1000r/min stir 5 minutes, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into 4 parts of equivalent, obtain mixed liquor F1,
Mixed liquor F2, mixed liquor F3, mixed liquor F4；
(27) 2.6mL tetraethyl orthosilicate and 13mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G1；
(28) material O is added in mixed liquor G1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain Substance P 1, Substance P 1 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P 2；
(29) 2.8mL tetraethyl orthosilicate and 15mL acetylacetone,2,4-pentanedione are added in mixed liquor F2, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G2；
(30) Substance P 2 is added in mixed liquor G2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains Substance P 3, Substance P 3 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P 4；
(31) 3.0mL tetraethyl orthosilicate and 17mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G3；
(32) Substance P 4 is added in mixed liquor G3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains Substance P 5, Substance P 5 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P 6；
(33) 3.2mL tetraethyl orthosilicate and 19mL acetylacetone,2,4-pentanedione are added in mixed liquor F4, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G4；
(34) Substance P 6 is added in mixed liquor G4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains Substance P 7, Substance P 7 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P；
(35) by 7.35 grams of NbCl4It is added to volume with the sodium citrate solution that 800mL mass percent concentration is 10%
For, in 1000mL conical flask, stirring 3 minutes under the conditions of 1000r/min, being divided into 4 parts of equivalent after shaking up, obtain mixed liquor H1, mix
Close liquid H2, mixed liquor H3, mixed liquor H4；
(36) MnCl for 0.36mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.75mol/L's
CeCl3Solution is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(37) Substance P is added in mixed liquor J1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material Q1, material Q1 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q2；
(38) MnCl for 0.56mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.55mol/L's
CeCl3Solution is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(39) material Q2 is added in mixed liquor J2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q3, material Q3 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q4；
(40) MnCl for 0.76mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.35mol/L's
CeCl3Solution is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(41) material Q4 is added in mixed liquor J3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q5, material Q5 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q6；
(42) MnCl for 0.96mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.15mol/L's
CeCl3Solution is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(43) material Q6 is added in mixed liquor J4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q7, material Q7 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q；
(44) by 32.07 grams of CuCl2With 12.39 grams of AlCl3It is added in 800mL deionized water, in 1000r/min condition
Lower stirring 10 minutes, is divided into 5 parts of equivalent, obtains mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4, mixed liquor after shaking up
K5；
(45) by 14.04 grams of NaOH and 11.22 gram of Na2CO3It is added in 800mL deionized water, in 1000r/min condition
Lower stirring 10 minutes, is divided into 5 parts of equivalent, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4, mixed liquor after shaking up
L5；
(46) under 1000r/min stirring condition, mixed liquor L1 is added drop-wise in mixed liquor K1, obtains mixed liquor X1, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X1～
10.0, obtain mixed liquor Y1；
(47) ZnCl for 0.27mol/L by 40mL molar concentration2Solution is added in mixed liquor Y1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z1；
(48) material Q is added in mixed liquor Z1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material R1, material R1 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R2；
(49) under 1000r/min stirring condition, mixed liquor L2 is added drop-wise in mixed liquor K2, obtains mixed liquor X2, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X2～
10.0, obtain mixed liquor Y2；
(50) ZnCl for 0.47mol/L by 50mL molar concentration2Solution is added in mixed liquor Y2, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z2；
(51) material R2 is added in mixed liquor Z2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R3, material R3 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R4；
(52) under 1000r/min stirring condition, mixed liquor L3 is added drop-wise in mixed liquor K3, obtains mixed liquor X3, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X3～
10.0, obtain mixed liquor Y3；
(53) ZnCl for 0.67mol/L by 60mL molar concentration2Solution is added in mixed liquor Y3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z3；
(54) material R4 is added in mixed liquor Z3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R5, material R5 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R6；
(55) under 1000r/min stirring condition, mixed liquor L4 is added drop-wise in mixed liquor K4, obtains mixed liquor X4, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X4～
10.0, obtain mixed liquor Y4；
(56) ZnCl for 0.87mol/L by 70mL molar concentration2Solution is added in mixed liquor Y4, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z4；
(57) material R6 is added in mixed liquor Z4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R7, material R7 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R8；
(58) under 1000r/min stirring condition, mixed liquor L5 is added drop-wise in mixed liquor K5, obtains mixed liquor X5, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X5～
10.0, obtain mixed liquor Y5；
(59) ZnCl for 1.07mol/L by 80mL molar concentration2Solution is added in mixed liquor Y5, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z5；
(60) material R8 is added in mixed liquor Z5, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R9, material R9 is after the washing with alcohol that 100mL mass percent concentration is 95% 68
DEG C drying baker in place 115 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, the material obtaining is
It is the support type ceramic catalyst removing acrylonitrile for supercritical water oxidation.
The support type ceramic catalytic that for supercritical water oxidation remove acrylonitrile that with the inventive method be obtained is presented herein below
Agent has carried out oxidative degradation test to the waste water containing acrylonitrile in afterflow fixed bed supercritical reaction device, further illustrates this
Invention.
The support type ceramic catalyst that the inventive method is obtained is seated in continuously in current flow fixed bed supercritical water reaction device,
Degrading experiment is carried out to the waste water containing acrylonitrile, result shows that the continuous stream being filled with this support type ceramic catalyst is fixed
Bed supercritical water reaction device can efficiently remove the acrylonitrile in waste water, when the acrylonitrile concentration in waste water is 48.1mg/L,
It is 365 DEG C in temperature, pressure is 26MPa, and the time of staying is the acrylonitrile concentration under the reaction condition of 40 seconds, in water outlet after process
It is reduced to 4.6mg/L.
Claims (1)
1. a kind of support type ceramic catalyst for supercritical water oxidation removal acrylonitrile is it is characterised in that prepare this catalysis
The comprising the following steps that of agent method：
(1) put into after the 149g ceramic particle 300mL deionized water wash being 4～6mm by particle diameter in 500mL acetone and soak
1h, removes liquid and obtains material M0, material M0 obtains material M1 after 300mL deionized water wash, and material M1 is put after filtration
Enter in the hydrochloric acid solution being 2.5mol/L to 300mL molar concentration and soak 0.5h, remove liquid after filtration and obtain material M2, material
In 85 DEG C of drying baker after M2 300mL deionized water wash, then the washing with alcohol being 95% with 500mL mass percent concentration
Middle placement 1.5h, obtains material M3, and material M3 is added to the AgNO that 250mL molar concentration is 4.33mol/L3In solution,
Temperature is to shake 75 minutes in 65 DEG C of shaking table, is filtered to remove liquid and obtains material M4, material M4 is through 100mL after being cooled to room temperature
Mass percent concentration be 97% washing with alcohol after in 76 DEG C of drying baker place 140 minutes, be subsequently placed in Muffle furnace
Roasting 72 minutes under the conditions of 488 DEG C, obtain material M；
(2) 5.66 grams of Polyvinylpyrrolidone and methanol solution that 650mL mass percent concentration is 80% are added to volume
For in 1000mL conical flask, stir 10 minutes under the conditions of 1000r/min, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor A 1,
Mixed liquor A 2, mixed liquor A 3, mixed liquor A 4, mixed liquor A 5；
(3) 0.8563 gram of palladium chloride and 200mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 DEG C in temperature
In water-bath shake 20 minutes, then in 120 DEG C of drying baker place 140 minutes, after being cooled to room temperature add 200mL go from
Sub- water, stirs 3 minutes under the conditions of 1000r/min, is divided into 5 parts of equivalent after shaking up, and obtains mixed liquid B 1, mixed liquid B 2, mixing
Liquid B3, mixed liquid B 4, mixed liquid B 5；
(4) 3.27 gram of three hydrate ruthenium trichloride and 850mL deionized water being added to volume is in 1000mL conical flask,
Under the conditions of 1000r/min stir 3 minutes, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor A B1, mixed liquor A B2, mixed liquor A B3,
Mixed liquor A B4, mixed liquor A B5；
(5) sodium borohydride solution being 0.69mol/L by mixed liquor A 1, mixed liquor A B1 and 15mL molar concentration is added to mixing
In liquid B1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(6) material M is added in mixed liquor C1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material N1, material N1 is dry at 68 DEG C after the washing with alcohol that 100mL mass percent concentration is 95%
Place 115 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N2；
(7) sodium borohydride solution being 0.64mol/L by mixed liquor A 2, mixed liquor A B2 and 13mL molar concentration is added to mixing
In liquid B2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(8) material N2 is added in mixed liquor C2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material N3, material N3 is dry at 68 DEG C after the washing with alcohol that 100mL mass percent concentration is 95%
Place 115 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N4；
(9) sodium borohydride solution being 0.59mol/L by mixed liquor A 3, mixed liquor A B3 and 11mL molar concentration is added to mixing
In liquid B3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(10) material N4 is added in mixed liquor C3, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material N5, material N5 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N6；
(11) sodium borohydride solution being 0.54mol/L by mixed liquor A 4, mixed liquor A B4 and 9mL molar concentration is added to mixing
In liquid B4, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C4；
(12) material N6 is added in mixed liquor C4, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material N7, material N7 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N8；
(13) sodium borohydride solution being 0.49mol/L by mixed liquor A 5, mixed liquor A B5 and 7mL molar concentration is added to mixing
In liquid B5, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C5；
(14) material N8 is added in mixed liquor C5, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material N9, material N9 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material N；
(15) by 6.33 grams of PbCl2With 8.88 grams of NiCl2It is added in 850mL ethanol, under the conditions of 1000r/min, stir 3 points
Clock, adds 5mL concentrated nitric acid, is divided into 5 parts of equivalent after shaking up, and obtains mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4, mixes
Close liquid D5；
(16) 3.94 grams of carbamide and 0.59 gram of ammonium fluoride are added in mixed liquor D1, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E1；
(17) material N is added in mixed liquor E1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material O1, material O1 is dry at 68 DEG C after the washing with alcohol that 100mL mass percent concentration is 95%
Place 115 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O2；
(18) 3.84 grams of carbamide and 0.57 gram of ammonium fluoride are added in mixed liquor D2, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E2；
(19) material O2 is added in mixed liquor E2, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material O3, material O3 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O4；
(20) 3.74 grams of carbamide and 0.55 gram of ammonium fluoride are added in mixed liquor D3, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E3；
(21) material O4 is added in mixed liquor E3, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material O5, material O5 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O6；
(22) 3.64 grams of carbamide and 0.53 gram of ammonium fluoride are added in mixed liquor D4, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E4；
(23) material O6 is added in mixed liquor E4, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material O7, material O7 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O8；
(24) 3.54 grams of carbamide and 0.51 gram of ammonium fluoride are added in mixed liquor D5, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E5；
(25) material O8 is added in mixed liquor E5, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material O9, material O9 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material O；
(26) by positive for 5.37 grams of metatitanic acids four fourth fat being added in 800mL dehydrated alcohol under 1000r/min stirring condition,
Stir 5 minutes under the conditions of 1000r/min, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into 4 parts of equivalent, obtain mixed liquor F1, mix
Close liquid F2, mixed liquor F3, mixed liquor F4；
(27) 2.6mL tetraethyl orthosilicate and 13mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, stir under the conditions of 1000r/min
Mix 3 minutes, obtain mixed liquor G1；
(28) material O is added in mixed liquor G1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain Substance P 1, Substance P 1 is dry at 68 DEG C after the washing with alcohol that 100mL mass percent concentration is 95%
Place 115 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P 2；
(29) 2.8mL tetraethyl orthosilicate and 15mL acetylacetone,2,4-pentanedione are added in mixed liquor F2, stir under the conditions of 1000r/min
Mix 3 minutes, obtain mixed liquor G2；
(30) Substance P 2 is added in mixed liquor G2, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains Substance P 3, Substance P 3 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P 4；
(31) 3.0mL tetraethyl orthosilicate and 17mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, stir under the conditions of 1000r/min
Mix 3 minutes, obtain mixed liquor G3；
(32) Substance P 4 is added in mixed liquor G3, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains Substance P 5, Substance P 5 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P 6；
(33) 3.2mL tetraethyl orthosilicate and 19mL acetylacetone,2,4-pentanedione are added in mixed liquor F4, stir under the conditions of 1000r/min
Mix 3 minutes, obtain mixed liquor G4；
(34) Substance P 6 is added in mixed liquor G4, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains Substance P 7, Substance P 7 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain Substance P；
(35) by 7.35 grams of NbCl4Being added to volume with the sodium citrate solution that 800mL mass percent concentration is 10% is
In 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, be divided into 4 parts of equivalent after shaking up, obtain mixed liquor H1, mixing
Liquid H2, mixed liquor H3, mixed liquor H4；
(36) MnCl for 0.36mol/L by 30mL molar concentration2Solution and 70mL molar concentration are the CeCl of 0.75mol/L3Molten
Liquid is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(37) Substance P is added in mixed liquor J1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material Q1, material Q1 is dry at 68 DEG C after the washing with alcohol that 100mL mass percent concentration is 95%
Place 115 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q2；
(38) MnCl for 0.56mol/L by 40mL molar concentration2Solution and 60mL molar concentration are the CeCl of 0.55mol/L3Molten
Liquid is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(39) material Q2 is added in mixed liquor J2, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material Q3, material Q3 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q4；
(40) MnCl for 0.76mol/L by 50mL molar concentration2Solution and 50mL molar concentration are the CeCl of 0.35mol/L3Molten
Liquid is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(41) material Q4 is added in mixed liquor J3, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material Q5, material Q5 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q6；
(42) MnCl for 0.96mol/L by 60mL molar concentration2Solution and 40mL molar concentration are the CeCl of 0.15mol/L3Molten
Liquid is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(43) material Q6 is added in mixed liquor J4, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material Q7, material Q7 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material Q；
(44) by 32.07 grams of CuCl2With 12.39 grams of AlCl3It is added in 800mL deionized water, stir under the conditions of 1000r/min
Mix 10 minutes, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4, mixed liquor K5；
(45) by 14.04 grams of NaOH and 11.22 gram of Na2CO3It is added in 800mL deionized water, stir under the conditions of 1000r/min
Mix 10 minutes, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4, mixed liquor L5；
(46) under 1000r/min stirring condition, mixed liquor L1 is added drop-wise in mixed liquor K1, obtains mixed liquor X1, dense with mole
Spend the hydrochloric acid solution for 0.01mol/L and the pH value of mixed liquor X1 is adjusted to 9.5～10.0 by the NaOH solution of 0.01mol/L, obtain
To mixed liquor Y1；
(47) ZnCl for 0.27mol/L by 40mL molar concentration2Solution is added in mixed liquor Y1, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z1；
(48) material Q is added in mixed liquor Z1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material R1, material R1 is dry at 68 DEG C after the washing with alcohol that 100mL mass percent concentration is 95%
Place 115 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R2；
(49) under 1000r/min stirring condition, mixed liquor L2 is added drop-wise in mixed liquor K2, obtains mixed liquor X2, dense with mole
Spend the hydrochloric acid solution for 0.01mol/L and the pH value of mixed liquor X2 is adjusted to 9.5～10.0 by the NaOH solution of 0.01mol/L, obtain
To mixed liquor Y2；
(50) ZnCl for 0.47mol/L by 50mL molar concentration2Solution is added in mixed liquor Y2, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z2；
(51) material R2 is added in mixed liquor Z2, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material R3, material R3 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R4；
(52) under 1000r/min stirring condition, mixed liquor L3 is added drop-wise in mixed liquor K3, obtains mixed liquor X3, dense with mole
Spend the hydrochloric acid solution for 0.01mol/L and the pH value of mixed liquor X3 is adjusted to 9.5～10.0 by the NaOH solution of 0.01mol/L, obtain
To mixed liquor Y3；
(53) ZnCl for 0.67mol/L by 60mL molar concentration2Solution is added in mixed liquor Y3, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z3；
(54) material R4 is added in mixed liquor Z3, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material R5, material R5 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R6；
(55) under 1000r/min stirring condition, mixed liquor L4 is added drop-wise in mixed liquor K4, obtains mixed liquor X4, dense with mole
Spend the hydrochloric acid solution for 0.01mol/L and the pH value of mixed liquor X4 is adjusted to 9.5～10.0 by the NaOH solution of 0.01mol/L, obtain
To mixed liquor Y4；
(56) ZnCl for 0.87mol/L by 70mL molar concentration2Solution is added in mixed liquor Y4, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z4；
(57) material R6 is added in mixed liquor Z4, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material R7, material R7 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, obtain material R8；
(58) under 1000r/min stirring condition, mixed liquor L5 is added drop-wise in mixed liquor K5, obtains mixed liquor X5, dense with mole
Spend the hydrochloric acid solution for 0.01mol/L and the pH value of mixed liquor X5 is adjusted to 9.5～10.0 by the NaOH solution of 0.01mol/L, obtain
To mixed liquor Y5；
(59) ZnCl for 1.07mol/L by 80mL molar concentration2Solution is added in mixed liquor Y5, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z5；
(60) material R8 is added in mixed liquor Z5, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material R9, material R9 is after the washing with alcohol that 100mL mass percent concentration is 95% at 68 DEG C
Place 115 minutes in drying baker, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 487 DEG C, the material obtaining is to be used
Remove the support type ceramic catalyst of acrylonitrile in supercritical water oxidation.
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|---|---|---|---|---|
| CN107986431A (en) * | 2017-12-04 | 2018-05-04 | 北京中科宇清环保有限公司 | A kind of polyurethane catalytic filler for electric field-enhanced oxygen-enriching device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686521A (en) * | 2009-12-22 | 2012-09-19 | 株式会社日本触媒 | Catalyst for treatment of waste water, and method for treatment of waste water using the catalyst |
-
2016
- 2016-10-14 CN CN201610899786.4A patent/CN106378152A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686521A (en) * | 2009-12-22 | 2012-09-19 | 株式会社日本触媒 | Catalyst for treatment of waste water, and method for treatment of waste water using the catalyst |
Non-Patent Citations (6)
| Title |
|---|
| 何晓文等: "《水体污染处理新技术及应用》", 31 March 2013, 中国科学技术大学出版社 * |
| 周振等: "《水化学》", 31 August 2013, 冶金工业出版社 * |
| 王懿萍 等: "《工程化学实验》", 30 June 2009, 西南交通大学出版社 * |
| 祁鲁梁 等: "《水处理药剂及材料实用手册（第二版）》", 30 March 2006, 中国石化出版社 * |
| 胡昌义 等: "《一维氧化钛纳米材料》", 30 September 2015, 中南大学出版社 * |
| 雷乐成 等: "《水处理高级氧化技术》", 31 August 2001, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107986431A (en) * | 2017-12-04 | 2018-05-04 | 北京中科宇清环保有限公司 | A kind of polyurethane catalytic filler for electric field-enhanced oxygen-enriching device |
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