CN106378151A - Supported vanadium pentoxide catalyst for removing acrylonitrile by supercritical water oxidation - Google Patents
Supported vanadium pentoxide catalyst for removing acrylonitrile by 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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- B01J23/8986—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- 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
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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 vanadium pentoxide catalyst for removing acrylonitrile by supercritical water oxidation. Vanadium pentoxide is cleaned and then is modified by AgNO3 to obtain a substance M; the substance M modifies a mixed solution prepared from polyvinylpyrrolidone, methanol, palladium dichloride, rhodium chloride trihydrate, concentrated hydrochloric acid and sodium borohydride to obtain a substance N; the substance N modifies a mixed solution prepared from MnCl2, CoCl2, concentrated nitric acid, urea and ammonium fluoride to obtain a substance O; the substance O modifies a mixed solution prepared from tetrabutyl titanate, tetraethyl orthosilicate and acetylacetone to obtain a substance P; the substance P modifies a mixed solution prepared from ZrCl4, ZrCl2 and CeCl3 to obtain a substance Q; the substance Q modifies a mixed solution prepared from PbCl2, BiCl3, NaOH, Na2CO3 and MgCl2 to obtain a substance, namely the supported vanadium pentoxide catalyst for removing the acrylonitrile by the 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 vanadium pentoxide 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 vanadic anhydride removing acrylonitrile for supercritical water oxidation is urged
Agent, the comprising the following steps that of its preparation method：
(1) put into 500mL third after the 142g vanadium oxide particles 300mL deionized water wash being 4～6mm by particle diameter
Soak 1h in ketone, remove liquid after filtration and obtain material M0, material M0 obtains material M1 after 300mL deionized water wash, will
Material M1 puts in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L and soaks 0.5h, removes liquid and obtain thing after filtration
Matter M2,85 after material M2 300mL deionized water wash, then the washing with alcohol being 95% with 500mL mass percent concentration
DEG C drying baker in place 1.5h, obtain material M3, by material M3 be added to 250mL molar concentration be 3.55mol/L AgNO3
In 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 places 140 minutes after the washing with alcohol that 100mL mass percent concentration is 97% in 76 DEG C of drying baker, is subsequently placed in
In Muffle furnace under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 4.08 grams of Polyvinylpyrrolidone and methanol solution that 600mL mass percent concentration is 80% are added to
Volume is in 1000mL conical flask, stirs 10 minutes, be divided into 3 parts of equivalent, obtain mixed liquor after shaking up under the conditions of 1000r/min
A1, mixed liquor A 2, mixed liquor A 3；
(3) 0.9647 gram of palladium chloride and 180mL 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 3 parts of equivalent after shaking up, obtain mixed liquid B 1, mixed liquid B 2,
Mixed liquid B 3；
(4) 2.51 gram of three rhodium trichloride hydrate and 750mL deionized water being added to volume is in 1000mL conical flask,
Stir 3 minutes under the conditions of 1000r/min, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor A B1, mixed liquor A B2, mixed liquor A B3；
(5) sodium borohydride solution being 0.63mol/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 0.53mol/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 0.43mol/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 N；
(11) by 6.37 grams of MnCl2With 7.58 grams of CoCl2It 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；
(12) 5.64 grams of carbamide and 0.58 gram of ammonium fluoride are added in mixed liquor D1, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E1；
(13) 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；
(14) 5.54 grams of carbamide and 0.53 gram of ammonium fluoride are added in mixed liquor D2, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E2；
(15) 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；
(16) 5.44 grams of carbamide and 0.48 gram of ammonium fluoride are added in mixed liquor D3, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E3；
(17) 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；
(18) 5.34 grams of carbamide and 0.43 gram of ammonium fluoride are added in mixed liquor D4, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E4；
(19) 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；
(20) 5.24 grams of carbamide and 0.38 gram of ammonium fluoride are added in mixed liquor D5, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E5；
(21) 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；
(22) by positive for 6.29 grams of metatitanic acids four fourth fat being added in 750mL 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 3 parts of equivalent, obtain mixed liquor F1,
Mixed liquor F2, mixed liquor F3；
(23) 3.9mL tetraethyl orthosilicate and 14mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G1；
(24) 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；
(25) 3.6mL tetraethyl orthosilicate and 16mL acetylacetone,2,4-pentanedione are added in mixed liquor F2, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G2；
(26) 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；
(27) 3.3mL tetraethyl orthosilicate and 18mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G3；
(28) 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；
(29) by 6.35 grams of ZrCl4It 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；
(30) ZnCl for 0.25mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.90mol/L's
CeCl3Solution is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(31) 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；
(32) ZnCl for 0.45mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.70mol/L's
CeCl3Solution is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(33) 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；
(34) ZnCl for 0.65mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.50mol/L's
CeCl3Solution is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(35) 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；
(36) ZnCl for 0.85mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.30mol/L's
CeCl3Solution is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(37) 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；
(38) by 31.29 grams of PbCl2With 11.24 grams of BiCl3It is added in 800mL deionized water, in 1000r/min condition
Lower stirring 10 minutes, is divided into 4 parts of equivalent, obtains mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4 after shaking up；
(39) by 14.09 grams of NaOH and 11.54 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 after shaking up；
(40) 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；
(41) MgCl for 0.18mol/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；
(42) 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；
(43) 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；
(44) MgCl for 0.38mol/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；
(45) 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；
(46) 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；
(47) MgCl for 0.58mol/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；
(48) 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；
(49) 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；
(50) MgCl for 0.78mol/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；
(51) 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, the material obtaining is
It is the support type vanadium pentoxide catalyst removing acrylonitrile for supercritical water oxidation.
The invention has the beneficial effects as follows, the prepared support type vanadic anhydride removing acrylonitrile for supercritical water oxidation
Catalyst has 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 vanadium pentoxide catalyst removing acrylonitrile for supercritical water oxidation, below
Illustrate in fact to apply process by an example.
Embodiment 1.
(1) put into 500mL third after the 142g vanadium oxide particles 300mL deionized water wash being 4～6mm by particle diameter
Soak 1h in ketone, remove liquid after filtration and obtain material M0, material M0 obtains material M1 after 300mL deionized water wash, will
Material M1 puts in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L and soaks 0.5h, removes liquid and obtain thing after filtration
Matter M2,85 after material M2 300mL deionized water wash, then the washing with alcohol being 95% with 500mL mass percent concentration
DEG C drying baker in place 1.5h, obtain material M3, by material M3 be added to 250mL molar concentration be 3.55mol/L AgNO3
In 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 places 140 minutes after the washing with alcohol that 100mL mass percent concentration is 97% in 76 DEG C of drying baker, is subsequently placed in
In Muffle furnace under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 4.08 grams of Polyvinylpyrrolidone and methanol solution that 600mL mass percent concentration is 80% are added to
Volume is in 1000mL conical flask, stirs 10 minutes, be divided into 3 parts of equivalent, obtain mixed liquor after shaking up under the conditions of 1000r/min
A1, mixed liquor A 2, mixed liquor A 3；
(3) 0.9647 gram of palladium chloride and 180mL 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 3 parts of equivalent after shaking up, obtain mixed liquid B 1, mixed liquid B 2,
Mixed liquid B 3；
(4) 2.51 gram of three rhodium trichloride hydrate and 750mL deionized water being added to volume is in 1000mL conical flask,
Stir 3 minutes under the conditions of 1000r/min, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor A B1, mixed liquor A B2, mixed liquor A B3；
(5) sodium borohydride solution being 0.63mol/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 0.53mol/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 0.43mol/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 N；
(11) by 6.37 grams of MnCl2With 7.58 grams of CoCl2It 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；
(12) 5.64 grams of carbamide and 0.58 gram of ammonium fluoride are added in mixed liquor D1, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E1；
(13) 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；
(14) 5.54 grams of carbamide and 0.53 gram of ammonium fluoride are added in mixed liquor D2, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E2；
(15) 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；
(16) 5.44 grams of carbamide and 0.48 gram of ammonium fluoride are added in mixed liquor D3, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E3；
(17) 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；
(18) 5.34 grams of carbamide and 0.43 gram of ammonium fluoride are added in mixed liquor D4, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E4；
(19) 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；
(20) 5.24 grams of carbamide and 0.38 gram of ammonium fluoride are added in mixed liquor D5, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E5；
(21) 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；
(22) by positive for 6.29 grams of metatitanic acids four fourth fat being added in 750mL 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 3 parts of equivalent, obtain mixed liquor F1,
Mixed liquor F2, mixed liquor F3；
(23) 3.9mL tetraethyl orthosilicate and 14mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G1；
(24) 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；
(25) 3.6mL tetraethyl orthosilicate and 16mL acetylacetone,2,4-pentanedione are added in mixed liquor F2, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G2；
(26) 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；
(27) 3.3mL tetraethyl orthosilicate and 18mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G3；
(28) 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；
(29) by 6.35 grams of ZrCl4It 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；
(30) ZnCl for 0.25mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.90mol/L's
CeCl3Solution is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(31) 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；
(32) ZnCl for 0.45mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.70mol/L's
CeCl3Solution is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(33) 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；
(34) ZnCl for 0.65mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.50mol/L's
CeCl3Solution is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(35) 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；
(36) ZnCl for 0.85mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.30mol/L's
CeCl3Solution is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(37) 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；
(38) by 31.29 grams of PbCl2With 11.24 grams of BiCl3It is added in 800mL deionized water, in 1000r/min condition
Lower stirring 10 minutes, is divided into 4 parts of equivalent, obtains mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4 after shaking up；
(39) by 14.09 grams of NaOH and 11.54 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 after shaking up；
(40) 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；
(41) MgCl for 0.18mol/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；
(42) 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；
(43) 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；
(44) MgCl for 0.38mol/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；
(45) 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；
(46) 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；
(47) MgCl for 0.58mol/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；
(48) 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；
(49) 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；
(50) MgCl for 0.78mol/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；
(51) 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, the material obtaining is
It is the support type vanadium pentoxide catalyst removing acrylonitrile for supercritical water oxidation.
Support type five oxidation two that for supercritical water oxidation remove acrylonitrile that with the inventive method be obtained is presented herein below
Vanadium catalyst has carried out oxidative degradation test to the waste water containing acrylonitrile in afterflow fixed bed supercritical reaction device, further
The present invention is described.
It is anti-that the support type vanadium pentoxide catalyst that the inventive method is obtained is seated in continuously current flow fixed bed supercritical water
Answer in device, Degrading experiment has been carried out to the waste water containing acrylonitrile, result shows to be filled with the catalysis of this support type vanadic anhydride
The continuously current flow fixed bed supercritical water reaction device of agent can efficiently remove the acrylonitrile in waste water, when the acrylonitrile concentration in waste water
During for 48.1mg/L, it is 365 DEG C in temperature, pressure is 26MPa, and the time of staying is water outlet after process under the reaction condition of 40 seconds
In acrylonitrile concentration be reduced to 3.6mg/L.
Claims (1)
1. a kind of support type vanadium pentoxide catalyst for supercritical water oxidation removal acrylonitrile is it is characterised in that prepare
The comprising the following steps that of this catalyst method：
(1) put in 500mL acetone after the 142g vanadium oxide particles 300mL deionized water wash being 4～6mm by particle diameter
Soak 1h, remove liquid after filtration and obtain material M0, material M0 obtains material M1 after 300mL deionized water wash, by material
M1 puts in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L and soaks 0.5h, removes liquid and obtain material M2 after filtration,
Dry at 85 DEG C after material M2 300mL deionized water wash, then the washing with alcohol being 95% with 500mL mass percent concentration
Place 1.5h in dry case, obtain material M3, material M3 is added to the AgNO that 250mL molar concentration is 3.55mol/L3Solution
In, 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) 4.08 grams of Polyvinylpyrrolidone and methanol solution that 600mL 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 3 parts of equivalent, obtain mixed liquor A 1,
Mixed liquor A 2, mixed liquor A 3；
(3) 0.9647 gram of palladium chloride and 180mL 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 3 parts of equivalent after shaking up, and obtains mixed liquid B 1, mixed liquid B 2, mixing
Liquid B3；
(4) 2.51 gram of three rhodium trichloride hydrate and 750mL deionized water being added to volume is in 1000mL conical flask,
Stir 3 minutes under the conditions of 1000r/min, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor A B1, mixed liquor A B2, mixed liquor A B3；
(5) sodium borohydride solution being 0.63mol/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 0.53mol/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 0.43mol/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 N；
(11) by 6.37 grams of MnCl2With 7.58 grams of CoCl2It 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；
(12) 5.64 grams of carbamide and 0.58 gram of ammonium fluoride are added in mixed liquor D1, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E1；
(13) 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；
(14) 5.54 grams of carbamide and 0.53 gram of ammonium fluoride are added in mixed liquor D2, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E2；
(15) 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；
(16) 5.44 grams of carbamide and 0.48 gram of ammonium fluoride are added in mixed liquor D3, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E3；
(17) 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；
(18) 5.34 grams of carbamide and 0.43 gram of ammonium fluoride are added in mixed liquor D4, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E4；
(19) 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；
(20) 5.24 grams of carbamide and 0.38 gram of ammonium fluoride are added in mixed liquor D5, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E5；
(21) 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；
(22) by positive for 6.29 grams of metatitanic acids four fourth fat being added in 750mL 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 3 parts of equivalent, obtain mixed liquor F1, mix
Close liquid F2, mixed liquor F3；
(23) 3.9mL tetraethyl orthosilicate and 14mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, stir under the conditions of 1000r/min
Mix 3 minutes, obtain mixed liquor G1；
(24) 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；
(25) 3.6mL tetraethyl orthosilicate and 16mL acetylacetone,2,4-pentanedione are added in mixed liquor F2, stir under the conditions of 1000r/min
Mix 3 minutes, obtain mixed liquor G2；
(26) 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；
(27) 3.3mL tetraethyl orthosilicate and 18mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, stir under the conditions of 1000r/min
Mix 3 minutes, obtain mixed liquor G3；
(28) 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；
(29) by 6.35 grams of ZrCl4Being 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；
(30) ZnCl for 0.25mol/L by 30mL molar concentration2Solution and 70mL molar concentration are the CeCl of 0.90mol/L3Molten
Liquid is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(31) 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；
(32) ZnCl for 0.45mol/L by 40mL molar concentration2Solution and 60mL molar concentration are the CeCl of 0.70mol/L3Molten
Liquid is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(33) 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；
(34) ZnCl for 0.65mol/L by 50mL molar concentration2Solution and 50mL molar concentration are the CeCl of 0.50mol/L3Molten
Liquid is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(35) 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；
(36) ZnCl for 0.85mol/L by 60mL molar concentration2Solution and 40mL molar concentration are the CeCl of 0.30mol/L3Molten
Liquid is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(37) 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；
(38) by 31.29 grams of PbCl2With 11.24 grams of BiCl3It is added in 800mL deionized water, stir under the conditions of 1000r/min
Mix 10 minutes, after shaking up, be divided into 4 parts of equivalent, obtain mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4；
(39) by 14.09 grams of NaOH and 11.54 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；
(40) 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；
(41) MgCl for 0.18mol/L by 40mL molar concentration2Solution is added in mixed liquor Y1, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z1；
(42) 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；
(43) 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；
(44) MgCl for 0.38mol/L by 50mL molar concentration2Solution is added in mixed liquor Y2, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z2；
(45) 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；
(46) 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；
(47) MgCl for 0.58mol/L by 60mL molar concentration2Solution is added in mixed liquor Y3, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z3；
(48) 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；
(49) 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；
(50) MgCl for 0.78mol/L by 70mL molar concentration2Solution is added in mixed liquor Y4, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z4；
(51) 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, the material obtaining is to be used
Remove the support type vanadium pentoxide catalyst of acrylonitrile in supercritical water oxidation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610896298.8A CN106378151A (en) | 2016-10-14 | 2016-10-14 | Supported vanadium pentoxide catalyst for removing acrylonitrile by supercritical water oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610896298.8A CN106378151A (en) | 2016-10-14 | 2016-10-14 | Supported vanadium pentoxide catalyst for removing acrylonitrile by supercritical water oxidation |
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Citations (1)
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 周振 等: "《水化学》", 31 August 2013, 冶金工业出版社 * |
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