CN106391092A - Loaded type zeolite catalyst for removing acrylamide through supercritical water oxidation - Google Patents
Loaded type zeolite catalyst for removing acrylamide through supercritical water oxidation Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—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 loaded type zeolite catalyst for removing acrylamide through supercritical water oxidation. Zeolite is cleaned and is then prepared into a substance M through the modification by AgNO3; the substance M is prepared into a substance N through the modification on a mixed solution prepared from polyvinylpyrrolidone, methyl alcohol, gold chloride, rhodium chloride trihydrate, rutheniumchloride hydrate, concentrated hydrochloric acid and sodium borohydride; the substance N is prepared into a substance O through the modification on a mixed solution prepared from CdCl2, ZnCl2, concentrated nitric acid, carbamide and ammonium fluoride; the substance O is prepared into a substance P through the modification on a mixed solution prepared from tetra-n-butyl titanate, tetraethoxysilane and acetylacetone; the substance P is prepared into a substance Q through the modification on a mixed solution prepared from ZrCl4, PbCl2 and BiCl3; the substance Q is prepared into a substance through the modification on a mixed solution prepared from NiCl2, InCl3, NaOH, Na2CO3 and MnCl2, and the substance is the loaded type zeolite catalyst for removing acrylamide 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 zeolite catalyst of critical oxidation removal acrylamide.
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 overcritical in oxidizing process
The good dissolubility to various organic matters and oxygen for the water, organic matter, 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 halide, sulphur and phosphorus change into sulfate and phosphate respectively, and organic nitrogen converts
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 managerial skills 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 researchers 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 acrylamide for supercritical water oxidation at present.
Content of the invention
It is an object of the invention to provide a kind of support type zeolite catalyst removing acrylamide for supercritical water oxidation,
The comprising the following steps that of its preparation method：
(1) put into leaching in 500mL acetone with 300mL deionized water after the 147g zeolite granular that particle diameter is 4～6mm being washed
Bubble 1h, removes liquid and obtains material M0, material M0 obtains material M1 after the washing of 300mL deionized water, 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
Matter M2 is washed with 300mL deionized water, then in 85 DEG C of drying after being washed with the ethanol that 500mL mass percent concentration is 95%
Place 1.5h in case, obtain material M3, material M3 is added to the AgNO that 250mL molar concentration is 2.78mol/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% ethanol washing after in 76 DEG C of drying box place 140 minutes, be subsequently placed in Muffle
In stove under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 3.65 grams of polyvinylpyrrolidones 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) 0.68 gram of gold trichloride and 200mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 DEG C in temperature
Water-bath in shake 20 minutes, then in 120 DEG C of drying box place 140 minutes, after being cooled to room temperature add 200mL go
Ionized 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, mixes
Close liquid B3, mixed liquid B 4, mixed liquid B 5；
(4) 2.87 gram of three rhodium trichloride hydrate, 3.99 gram of three hydrate ruthenium trichloride and 850mL deionized water are added to appearance
Amass as, in 1000mL conical flask, stirring 3 minutes under the conditions of 1000r/min, being divided into 5 parts of equivalent after shaking up, obtain mixed liquor
AB1, mixed liquor A B2, mixed liquor A B3, mixed liquor A B4, mixed liquor A B5；
(5) sodium borohydride solution being 0.97mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N2；
(7) sodium borohydride solution being 0.92mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N4；
(9) sodium borohydride solution being 0.87mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N6；
(11) sodium borohydride solution being 0.82mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N8；
(13) sodium borohydride solution being 0.77mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N；
(15) by 5.91 grams of CdCl2With 7.28 grams of ZnCl2It is added in 750mL ethanol, stir 3 under the conditions of 1000r/min
Minute, add 5mL red fuming nitric acid (RFNA), be divided into 3 parts of equivalent after shaking up, obtain mixed liquor D1, mixed liquor D2, mixed liquor D3；
(16) 5.94 grams of urea 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；
(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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material O2；
(18) 5.84 grams of urea 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；
(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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material O4；
(20) 5.74 grams of urea 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；
(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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material O；
(22) by positive for 4.55 grams of metatitanic acids four fourth fat being added in 750mL absolute ethyl alcohol under 1000r/min stirring condition,
Under the conditions of 1000r/min stir 5 minutes, be subsequently adding 4mL red fuming nitric acid (RFNA), after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor F1,
Mixed liquor F2, mixed liquor F3；
(23) 3.4mL 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；
(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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain Substance P 2；
(25) 3.1mL 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；
(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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain Substance P 4；
(27) 2.8mL 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；
(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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain Substance P；
(29) by 6.57 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) PbCl for 0.22mol/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；
(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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q2；
(32) PbCl for 0.42mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.65mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q4；
(34) PbCl for 0.62mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.55mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q6；
(36) PbCl for 0.82mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.45mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q；
(38) by 22.95 grams of ZnCl2With 9.97 grams of InCl3It is added in 800mL deionized water, under the conditions of 1000r/min
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；
(39) by 14.57 grams of NaOH and 11.28 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；
(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) MnCl for 0.20mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 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) MnCl for 0.40mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 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) MnCl for 0.60mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 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) MnCl for 0.80mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material R8；
(52) 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；
(53) MnCl for 1.00mol/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；
(54) 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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, the material obtaining is
It is the support type zeolite catalyst removing acrylamide for supercritical water oxidation.
The invention has the beneficial effects as follows, the prepared support type zeolite catalysis removing acrylamide for supercritical water oxidation
Agent has that stability is strong, active height, life-span length, high to acrylamide removal efficiency the features such as.
Specific embodiment
The present invention provides a kind of support type zeolite catalyst removing acrylamide for supercritical water oxidation, below by
One example is illustrating in fact to apply process.
Embodiment 1.
(1) put into leaching in 500mL acetone with 300mL deionized water after the 147g zeolite granular that particle diameter is 4～6mm being washed
Bubble 1h, removes liquid and obtains material M0, material M0 obtains material M1 after the washing of 300mL deionized water, 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
Matter M2 is washed with 300mL deionized water, then in 85 DEG C of drying after being washed with the ethanol that 500mL mass percent concentration is 95%
Place 1.5h in case, obtain material M3, material M3 is added to the AgNO that 250mL molar concentration is 2.78mol/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% ethanol washing after in 76 DEG C of drying box place 140 minutes, be subsequently placed in Muffle
In stove under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 3.65 grams of polyvinylpyrrolidones 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) 0.68 gram of gold trichloride and 200mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 DEG C in temperature
Water-bath in shake 20 minutes, then in 120 DEG C of drying box place 140 minutes, after being cooled to room temperature add 200mL go
Ionized 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, mixes
Close liquid B3, mixed liquid B 4, mixed liquid B 5；
(4) 2.87 gram of three rhodium trichloride hydrate, 3.99 gram of three hydrate ruthenium trichloride and 850mL deionized water are added to appearance
Amass as, in 1000mL conical flask, stirring 3 minutes under the conditions of 1000r/min, being divided into 5 parts of equivalent after shaking up, obtain mixed liquor
AB1, mixed liquor A B2, mixed liquor A B3, mixed liquor A B4, mixed liquor A B5；
(5) sodium borohydride solution being 0.97mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N2；
(7) sodium borohydride solution being 0.92mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N4；
(9) sodium borohydride solution being 0.87mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N6；
(11) sodium borohydride solution being 0.82mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N8；
(13) sodium borohydride solution being 0.77mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N；
(15) by 5.91 grams of CdCl2With 7.28 grams of ZnCl2It is added in 750mL ethanol, stir 3 under the conditions of 1000r/min
Minute, add 5mL red fuming nitric acid (RFNA), be divided into 3 parts of equivalent after shaking up, obtain mixed liquor D1, mixed liquor D2, mixed liquor D3；
(16) 5.94 grams of urea 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；
(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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material O2；
(18) 5.84 grams of urea 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；
(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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material O4；
(20) 5.74 grams of urea 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；
(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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material O；
(22) by positive for 4.55 grams of metatitanic acids four fourth fat being added in 750mL absolute ethyl alcohol under 1000r/min stirring condition,
Under the conditions of 1000r/min stir 5 minutes, be subsequently adding 4mL red fuming nitric acid (RFNA), after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor F1,
Mixed liquor F2, mixed liquor F3；
(23) 3.4mL 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；
(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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain Substance P 2；
(25) 3.1mL 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；
(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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain Substance P 4；
(27) 2.8mL 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；
(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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain Substance P；
(29) by 6.57 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) PbCl for 0.22mol/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；
(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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q2；
(32) PbCl for 0.42mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.65mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q4；
(34) PbCl for 0.62mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.55mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q6；
(36) PbCl for 0.82mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.45mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q；
(38) by 22.95 grams of ZnCl2With 9.97 grams of InCl3It is added in 800mL deionized water, under the conditions of 1000r/min
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；
(39) by 14.57 grams of NaOH and 11.28 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；
(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) MnCl for 0.20mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 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) MnCl for 0.40mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 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) MnCl for 0.60mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 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) MnCl for 0.80mol/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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material R8；
(52) 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；
(53) MnCl for 1.00mol/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；
(54) 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 ethanol washing that 100mL mass percent concentration is 95% 75
DEG C drying box in place 120 minutes, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, the material obtaining is
It is the support type zeolite catalyst removing acrylamide for supercritical water oxidation.
It is presented herein below and urge with the support type zeolite removing acrylamide for supercritical water oxidation that the inventive method is obtained
Agent has carried out oxidative degradation test to the waste water containing acrylamide in afterflow fixed bed supercritical reaction device, furtherly
The bright present invention.
The support type zeolite 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 acrylamide, result shows that the continuous stream being filled with this support type zeolite catalyst is solid
Fixed bed supercritical water reaction device can efficiently remove the acrylamide in waste water, when the acrylamide concentration in waste water is
During 42.9mg/L, it is 375 DEG C in temperature, pressure is 27MPa, and the time of staying is under the reaction condition of 30 seconds, in water outlet after process
Acrylamide concentration be reduced to 5.7mg/L.
Claims (1)
1. a kind of support type zeolite catalyst removing acrylamide for supercritical water oxidation is urged it is characterised in that preparing this
The comprising the following steps that of agent method：
(1) put into after the 147g zeolite granular that particle diameter is 4～6mm being washed with 300mL deionized water in 500mL acetone and soak
1h, removes liquid and obtains material M0, material M0 obtains material M1 after the washing of 300mL deionized water, 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
M2 is washed with 300mL deionized water, then in 85 DEG C of drying box after being washed with the ethanol that 500mL mass percent concentration is 95%
Middle placement 1.5h, obtains material M3, and material M3 is added to the AgNO that 250mL molar concentration is 2.78mol/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% ethanol washing after in 76 DEG C of drying box place 140 minutes, be subsequently placed in Muffle furnace
Roasting 72 minutes under the conditions of 488 DEG C, obtain material M；
(2) 3.65 grams of polyvinylpyrrolidones 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) 0.68 gram of gold trichloride and 200mL concentrated hydrochloric acid are entered to volume in 500mL conical flask, the water being 75 DEG C in temperature
Shake in bath 20 minutes, then place 140 minutes in 120 DEG C of drying box, after being cooled to room temperature, add 200mL deionization
Water, stirs 3 minutes under the conditions of 1000r/min, is divided into 5 parts of equivalent, obtains mixed liquid B 1, mixed liquid B 2, mixed liquor after shaking up
B3, mixed liquid B 4, mixed liquid B 5；
(4) 2.87 gram of three rhodium trichloride hydrate, 3.99 gram of three hydrate ruthenium trichloride and 850mL deionized water being added to volume is
In 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor A B1, mix
Close liquid AB2, mixed liquor A B3, mixed liquor A B4, mixed liquor A B5；
(5) sodium borohydride solution being 0.97mol/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 75 DEG C after the ethanol washing that 100mL mass percent concentration is 95%
Place 120 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N2；
(7) sodium borohydride solution being 0.92mol/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 75 DEG C after the ethanol washing that 100mL mass percent concentration is 95%
Place 120 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N4；
(9) sodium borohydride solution being 0.87mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N6；
(11) sodium borohydride solution being 0.82mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N8；
(13) sodium borohydride solution being 0.77mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material N；
(15) by 5.91 grams of CdCl2With 7.28 grams of ZnCl2It is added in 750mL ethanol, under the conditions of 1000r/min, stir 3 points
Clock, adds 5mL red fuming nitric acid (RFNA), is divided into 3 parts of equivalent, obtains mixed liquor D1, mixed liquor D2, mixed liquor D3 after shaking up；
(16) 5.94 grams of urea 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；
(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 75 DEG C after the ethanol washing that 100mL mass percent concentration is 95%
Place 120 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material O2；
(18) 5.84 grams of urea 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；
(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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material O4；
(20) 5.74 grams of urea 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；
(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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material O；
(22) by positive for 4.55 grams of metatitanic acids four fourth fat being added in 750mL absolute ethyl alcohol under 1000r/min stirring condition,
Stir 5 minutes under the conditions of 1000r/min, be subsequently adding 4mL red fuming nitric acid (RFNA), after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor F1, mix
Close liquid F2, mixed liquor F3；
(23) 3.4mL 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；
(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 75 DEG C after the ethanol washing that 100mL mass percent concentration is 95%
Place 120 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain Substance P 2；
(25) 3.1mL 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；
(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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain Substance P 4；
(27) 2.8mL 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；
(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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain Substance P；
(29) by 6.57 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) PbCl for 0.22mol/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；
(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 75 DEG C after the ethanol washing that 100mL mass percent concentration is 95%
Place 120 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q2；
(32) PbCl for 0.42mol/L by 40mL molar concentration2Solution and 60mL molar concentration are the CeCl of 0.65mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q4；
(34) PbCl for 0.62mol/L by 50mL molar concentration2Solution and 50mL molar concentration are the CeCl of 0.55mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q6；
(36) PbCl for 0.82mol/L by 60mL molar concentration2Solution and 40mL molar concentration are the CeCl of 0.45mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material Q；
(38) by 22.95 grams of ZnCl2With 9.97 grams of InCl3It is added in 800mL deionized water, stir under the conditions of 1000r/min
10 minutes, after shaking up, it is divided into 5 parts of equivalent, obtain mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4, mixed liquor K5；
(39) by 14.57 grams of NaOH and 11.28 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；
(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) MnCl for 0.20mol/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 75 DEG C after the ethanol washing that 100mL mass percent concentration is 95%
Place 120 minutes in dry case, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 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) MnCl for 0.40mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 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) MnCl for 0.60mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 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) MnCl for 0.80mol/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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, obtain material R8；
(52) 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；
(53) MnCl for 1.00mol/L by 80mL molar concentration2Solution is added in mixed liquor Y5, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z5；
(54) 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 ethanol washing that 100mL mass percent concentration is 95% at 75 DEG C
Place 120 minutes in drying box, be subsequently placed in Muffle furnace roasting 65 minutes under the conditions of 475 DEG C, the material obtaining is to be used
Remove the support type zeolite catalyst of acrylamide in supercritical water oxidation.
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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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| 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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