CN106423210A - Load-type foamed aluminum catalyst for removing dimethyl formamide by use of supercritical water oxidization - Google Patents

Load-type foamed aluminum catalyst for removing dimethyl formamide by use of supercritical water oxidization Download PDF

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CN106423210A
CN106423210A CN201610899815.7A CN201610899815A CN106423210A CN 106423210 A CN106423210 A CN 106423210A CN 201610899815 A CN201610899815 A CN 201610899815A CN 106423210 A CN106423210 A CN 106423210A
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不公告发明人
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Beijing Shimizu Environmental Protection Technology Co Ltd
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Beijing Shimizu Environmental Protection Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • 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
    • B01J23/8933—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
    • B01J23/8973—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 arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses a load-type foamed aluminum catalyst for removing dimethyl formamide by use of supercritical water oxidization. The load-type foamed aluminum catalyst for removing dimethyl formamide by use of supercritical water oxidization is prepared by virtue of the following steps: washing foamed aluminum, and then modifying the washed foamed aluminum with AgNO3, thereby obtaining a substance M; modifying a mixed solution prepared from polyvinyl pyrrolidone, methanol, gold trichloride, concentrated hydrochloric acid and sodium borohydride by the substance M, thereby obtaining a substance N; modifying a mixed solution prepared from SrCl2, CoCl2, concentrated aqua fortis, urea and ammonium fluoride by the substance N, thereby obtaining a substance O; modifying a mixed solution prepared from tetra-n-butyl titanate, tetraethyl orthosilicate and acetylacetone by the substance O, thereby obtaining a substance P; modifying a mixed solution prepared from ZrCl4, MgCl2 and InCl3 by the substance P, thereby obtaining a substance Q; and modifying a mixed solution prepared from PbCl2, BiCl3, NaOH, Na2CO3 and CdCl2 by the substance Q, thereby obtaining a substance, namely the load-type foamed aluminum catalyst for removing the dimethyl formamide by use of supercritical water oxidization.

Description

Remove the support type foam Al catalysts of dimethylformamide for supercritical water oxidation
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 foam Al catalysts of critical oxidation removal dimethylformamide.
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 catalysis removing dimethylformamide for supercritical water oxidation at present Agent.
Content of the invention
It is an object of the invention to provide a kind of support type foamed aluminium removing dimethylformamide for supercritical water oxidation Catalyst, the comprising the following steps that of its preparation method：
(1) put in 500mL acetone after the 89g foam alumina 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 2.27mol/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) 2.94 grams of Polyvinylpyrrolidone and methanol solution that 800mL mass percent concentration is 80% are added to Volume is in 1000mL conical flask, stirs 10 minutes, be divided into 4 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；
(3) 0.6217 gram of Auric chloride. and 200mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 in temperature DEG C water-bath in shake 20 minutes, then place 140 minutes in 120 DEG C of drying baker, be cooled to after room temperature and add 200mL Deionized water, under the conditions of 1000r/min stir 3 minutes, be divided into 4 parts of equivalent after shaking up, obtain mixed liquid B 1, mixed liquid B 2, Mixed liquid B 3, mixed liquid B 4；
(4) by mixed liquor A 1 and 15mL molar concentration, the sodium borohydride solution for 0.46mol/L is added in mixed liquid B 1, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(5) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N2；
(6) by mixed liquor A 2 and 13mL molar concentration, the sodium borohydride solution for 0.51mol/L is added in mixed liquid B 2, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(7) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N4；
(8) by mixed liquor A 3 and 11mL molar concentration, the sodium borohydride solution for 0.56mol/L is added in mixed liquid B 3, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(9) material N4 is added in mixed liquor C3, 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 N5, material N5 is after the washing with alcohol that 100mL mass percent concentration is 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N6；
(10) by mixed liquor A 4 and 9mL molar concentration, the sodium borohydride solution for 0.61mol/L is added in mixed liquid B 4, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C4；
(11) material N6 is added in mixed liquor C4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room It is filtered to remove liquid after temperature and obtains material N7, material N7 is after the washing with alcohol that 100mL mass percent concentration is 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N；
(12) by 5.27 grams of SrCl2With 7.18 grams of CoCl2It is added in 800mL ethanol, stir 3 under the conditions of 1000r/min Minute, add 5mL concentrated nitric acid, be divided into 4 parts of equivalent after shaking up, obtain mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4；
(13) 1.97 grams of carbamide and 0.31 gram of ammonium fluoride are added in mixed liquor D1, stir 3 under the conditions of 1000r/min Minute, obtain mixed liquor E1；
(14) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O2；
(15) 1.92 grams of carbamide and 0.29 gram of ammonium fluoride are added in mixed liquor D2, stir 3 under the conditions of 1000r/min Minute, obtain mixed liquor E2；
(16) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O4；
(17) 1.87 grams of carbamide and 0.27 gram of ammonium fluoride are added in mixed liquor D3, stir 3 under the conditions of 1000r/min Minute, obtain mixed liquor E3；
(18) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O6；
(19) 1.82 grams of carbamide and 0.25 gram of ammonium fluoride are added in mixed liquor D4, stir 3 under the conditions of 1000r/min Minute, obtain mixed liquor E4；
(20) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O；
(21) by positive for 4.29 grams of metatitanic acids four fourth fat being added in 700mL dehydrated alcohol under 1000r/min stirring condition, Under the conditions of 1000r/min stir 5 minutes, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into 4 parts of equivalent, obtain mixed liquor F1, Mixed liquor F2, mixed liquor F3, mixed liquor F4；
(22) 1.5mL tetraethyl orthosilicate and 9mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G1；
(23) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P 2；
(24) 1.8mL tetraethyl orthosilicate and 12mL acetylacetone,2,4-pentanedione are added in mixed liquor F2, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G2；
(25) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P 4；
(26) 2.1mL tetraethyl orthosilicate and 15mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G3；
(27) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P 6；
(28) 2.4mL tetraethyl orthosilicate and 18mL acetylacetone,2,4-pentanedione are added in mixed liquor F4, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G4；
(29) Substance P 6 is added in mixed liquor G4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room It is filtered to remove liquid after temperature and obtains Substance P 7, Substance P 7 is after the washing with alcohol that 100mL mass percent concentration is 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P；
(30) by 6.33 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；
(31) MgCl for 0.46mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.91mol/L's InCl3Solution is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(32) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q2；
(33) MgCl for 0.56mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.71mol/L's InCl3Solution is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(34) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q4；
(35) MgCl for 0.66mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.51mol/L's InCl3Solution is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(36) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q6；
(37) MgCl for 0.76mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.31mol/L's InCl3Solution is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(38) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q；
(39) by 26.34 grams of PbCl2With 9.54 grams of BiCl3It is added in 800mL deionized water, under the conditions of 1000r/min 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；
(40) by 11.28 grams of NaOH and 7.63 gram of Na2CO3It is added in 800mL deionized water, under the conditions of 1000r/min Stirring 10 minutes, is divided into 4 parts of equivalent, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4 after shaking up；
(41) 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；
(42) CdCl for 0.25mol/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；
(43) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material R2；
(44) 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；
(45) CdCl for 0.45mol/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；
(46) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material R4；
(47) 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；
(48) CdCl for 0.65mol/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；
(49) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material R6；
(50) 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；
(51) CdCl for 0.85mol/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；
(52) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, the material obtaining is It is the support type foam Al catalysts removing dimethylformamide for supercritical water oxidation.
The invention has the beneficial effects as follows, the prepared support type foam removing dimethylformamide for supercritical water oxidation Al catalysts have that stability is strong, active height, life-span length, high to dimethylformamide removal efficiency the features such as.
Specific embodiment
The present invention provides a kind of support type foam Al catalysts removing dimethylformamide for supercritical water oxidation, under Face illustrates in fact to apply process by an example.
Embodiment 1.
(1) put in 500mL acetone after the 89g foam alumina 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 2.27mol/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) 2.94 grams of Polyvinylpyrrolidone and methanol solution that 800mL mass percent concentration is 80% are added to Volume is in 1000mL conical flask, stirs 10 minutes, be divided into 4 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；
(3) 0.6217 gram of Auric chloride. and 200mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 in temperature DEG C water-bath in shake 20 minutes, then place 140 minutes in 120 DEG C of drying baker, be cooled to after room temperature and add 200mL Deionized water, under the conditions of 1000r/min stir 3 minutes, be divided into 4 parts of equivalent after shaking up, obtain mixed liquid B 1, mixed liquid B 2, Mixed liquid B 3, mixed liquid B 4；
(4) by mixed liquor A 1 and 15mL molar concentration, the sodium borohydride solution for 0.46mol/L is added in mixed liquid B 1, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(5) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N2；
(6) by mixed liquor A 2 and 13mL molar concentration, the sodium borohydride solution for 0.51mol/L is added in mixed liquid B 2, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(7) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N4；
(8) by mixed liquor A 3 and 11mL molar concentration, the sodium borohydride solution for 0.56mol/L is added in mixed liquid B 3, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(9) material N4 is added in mixed liquor C3, 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 N5, material N5 is after the washing with alcohol that 100mL mass percent concentration is 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N6；
(10) by mixed liquor A 4 and 9mL molar concentration, the sodium borohydride solution for 0.61mol/L is added in mixed liquid B 4, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C4；
(11) material N6 is added in mixed liquor C4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room It is filtered to remove liquid after temperature and obtains material N7, material N7 is after the washing with alcohol that 100mL mass percent concentration is 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N；
(12) by 5.27 grams of SrCl2With 7.18 grams of CoCl2It is added in 800mL ethanol, stir 3 under the conditions of 1000r/min Minute, add 5mL concentrated nitric acid, be divided into 4 parts of equivalent after shaking up, obtain mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4；
(13) 1.97 grams of carbamide and 0.31 gram of ammonium fluoride are added in mixed liquor D1, stir 3 under the conditions of 1000r/min Minute, obtain mixed liquor E1；
(14) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O2；
(15) 1.92 grams of carbamide and 0.29 gram of ammonium fluoride are added in mixed liquor D2, stir 3 under the conditions of 1000r/min Minute, obtain mixed liquor E2；
(16) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O4；
(17) 1.87 grams of carbamide and 0.27 gram of ammonium fluoride are added in mixed liquor D3, stir 3 under the conditions of 1000r/min Minute, obtain mixed liquor E3；
(18) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O6；
(19) 1.82 grams of carbamide and 0.25 gram of ammonium fluoride are added in mixed liquor D4, stir 3 under the conditions of 1000r/min Minute, obtain mixed liquor E4；
(20) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O；
(21) by positive for 4.29 grams of metatitanic acids four fourth fat being added in 700mL dehydrated alcohol under 1000r/min stirring condition, Under the conditions of 1000r/min stir 5 minutes, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into 4 parts of equivalent, obtain mixed liquor F1, Mixed liquor F2, mixed liquor F3, mixed liquor F4；
(22) 1.5mL tetraethyl orthosilicate and 9mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G1；
(23) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P 2；
(24) 1.8mL tetraethyl orthosilicate and 12mL acetylacetone,2,4-pentanedione are added in mixed liquor F2, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G2；
(25) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P 4；
(26) 2.1mL tetraethyl orthosilicate and 15mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G3；
(27) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P 6；
(28) 2.4mL tetraethyl orthosilicate and 18mL acetylacetone,2,4-pentanedione are added in mixed liquor F4, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G4；
(29) Substance P 6 is added in mixed liquor G4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room It is filtered to remove liquid after temperature and obtains Substance P 7, Substance P 7 is after the washing with alcohol that 100mL mass percent concentration is 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P；
(30) by 6.33 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；
(31) MgCl for 0.46mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.91mol/L's InCl3Solution is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(32) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q2；
(33) MgCl for 0.56mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.71mol/L's InCl3Solution is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(34) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q4；
(35) MgCl for 0.66mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.51mol/L's InCl3Solution is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(36) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q6；
(37) MgCl for 0.76mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.31mol/L's InCl3Solution is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(38) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q；
(39) by 26.34 grams of PbCl2With 9.54 grams of BiCl3It is added in 800mL deionized water, under the conditions of 1000r/min 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；
(40) by 11.28 grams of NaOH and 7.63 gram of Na2CO3It is added in 800mL deionized water, under the conditions of 1000r/min Stirring 10 minutes, is divided into 4 parts of equivalent, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4 after shaking up；
(41) 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；
(42) CdCl for 0.25mol/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；
(43) 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 92% at 65 DEG C Drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material R2；
(44) 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；
(45) CdCl for 0.45mol/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；
(46) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material R4；
(47) 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；
(48) CdCl for 0.65mol/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；
(49) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material R6；
(50) 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；
(51) CdCl for 0.85mol/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；
(52) 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 92% 65 DEG C drying baker in place 110 minutes, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, the material obtaining is It is the support type foam Al catalysts removing dimethylformamide for supercritical water oxidation.
The support type bubble that for supercritical water oxidation remove dimethylformamide that with the inventive method be obtained is presented herein below Foam Al catalysts have carried out oxidative degradation examination to the waste water containing dimethylformamide in afterflow fixed bed supercritical reaction device Test, further illustrate the present invention.
By the prepared support type foamed aluminium Catalyst packing of the inventive method in continuously current flow fixed bed supercritical water reaction device In, Degrading experiment is carried out to the waste water containing dimethylformamide, result shows to be filled with this support type foam Al catalysts Continuously current flow fixed bed supercritical water reaction device can efficiently remove dimethylformamide in waste water, when the dimethyl in waste water When concentration of forma is 36.4mg/L, it is 365 DEG C in temperature, pressure is 25.5MPa, and the time of staying is the reaction condition of 37 seconds Under, the dimethylformamide concentration in water outlet after process is reduced to 2.3mg/L.

Claims (1)

1. a kind of support type graphite catalyst for supercritical water oxidation removal dimethylformamide is it is characterised in that prepare The comprising the following steps that of this catalyst method：
(1) put into after the 89g foam alumina particles 300mL deionized water wash being 4～6mm by particle diameter in 500mL acetone and soak 1h, removes liquid and obtains material M0, material M0 obtains material M1 after 300mL deionized water wash, and material M1 is put after filtration Enter in the hydrochloric acid solution being 2.5mol/L to 300mL molar concentration and soak 0.5h, remove liquid after filtration and obtain material M2, material In 85 DEG C of drying baker after M2 300mL deionized water wash, then the washing with alcohol being 95% with 500mL mass percent concentration Middle placement 1.5h, obtains material M3, and material M3 is added to the AgNO that 250mL molar concentration is 2.27mol/L3In solution, Temperature is to shake 75 minutes in 65 DEG C of shaking table, is filtered to remove liquid and obtains material M4, material M4 is through 100mL after being cooled to room temperature Mass percent concentration be 97% washing with alcohol after in 76 DEG C of drying baker place 140 minutes, be subsequently placed in Muffle furnace Roasting 72 minutes under the conditions of 488 DEG C, obtain material M；
(2) 2.94 grams of Polyvinylpyrrolidone and methanol solution that 800mL 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 4 parts of equivalent, obtain mixed liquor A 1, Mixed liquor A 2, mixed liquor A 3, mixed liquor A 4；
(3) 0.6217 gram of Auric chloride. and 200mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 DEG C in temperature In water-bath shake 20 minutes, then in 120 DEG C of drying baker place 140 minutes, after being cooled to room temperature add 200mL go from Sub- water, stirs 3 minutes under the conditions of 1000r/min, is divided into 4 parts of equivalent after shaking up, and obtains mixed liquid B 1, mixed liquid B 2, mixing Liquid B3, mixed liquid B 4；
(4) by mixed liquor A 1 and 15mL molar concentration, the sodium borohydride solution for 0.46mol/L is added in mixed liquid B 1, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(5) 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 65 DEG C after the washing with alcohol that 100mL mass percent concentration is 92% Place 110 minutes in dry case, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N2；
(6) by mixed liquor A 2 and 13mL molar concentration, the sodium borohydride solution for 0.51mol/L is added in mixed liquid B 2, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(7) 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 65 DEG C after the washing with alcohol that 100mL mass percent concentration is 92% Place 110 minutes in dry case, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N4；
(8) by mixed liquor A 3 and 11mL molar concentration, the sodium borohydride solution for 0.56mol/L is added in mixed liquid B 3, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(9) material N4 is added in mixed liquor C3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature Filter liquid and obtain material N5, material N5 is dry at 65 DEG C after the washing with alcohol that 100mL mass percent concentration is 92% Place 110 minutes in dry case, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N6；
(10) by mixed liquor A 4 and 9mL molar concentration, the sodium borohydride solution for 0.61mol/L is added in mixed liquid B 4, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C4；
(11) material N6 is added in mixed liquor C4, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature It is filtered to remove liquid and obtains material N7, material N7 is after the washing with alcohol that 100mL mass percent concentration is 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material N；
(12) by 5.27 grams of SrCl2With 7.18 grams of CoCl2It is added in 800mL ethanol, under the conditions of 1000r/min, stir 3 points Clock, adds 5mL concentrated nitric acid, is divided into 4 parts of equivalent, obtains mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4 after shaking up；
(13) 1.97 grams of carbamide and 0.31 gram of ammonium fluoride are added in mixed liquor D1, under the conditions of 1000r/min, stir 3 points Clock, obtains mixed liquor E1；
(14) 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 65 DEG C after the washing with alcohol that 100mL mass percent concentration is 92% Place 110 minutes in dry case, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O2；
(15) 1.92 grams of carbamide and 0.29 gram of ammonium fluoride are added in mixed liquor D2, under the conditions of 1000r/min, stir 3 points Clock, obtains mixed liquor E2；
(16) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O4；
(17) 1.87 grams of carbamide and 0.27 gram of ammonium fluoride are added in mixed liquor D3, under the conditions of 1000r/min, stir 3 points Clock, obtains mixed liquor E3；
(18) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O6；
(19) 1.82 grams of carbamide and 0.25 gram of ammonium fluoride are added in mixed liquor D4, under the conditions of 1000r/min, stir 3 points Clock, obtains mixed liquor E4；
(20) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material O；
(21) by positive for 4.29 grams of metatitanic acids four fourth fat being added in 700mL dehydrated alcohol under 1000r/min stirring condition, Stir 5 minutes under the conditions of 1000r/min, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into 4 parts of equivalent, obtain mixed liquor F1, mix Close liquid F2, mixed liquor F3, mixed liquor F4；
(22) 1.5mL tetraethyl orthosilicate and 9mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, stir under the conditions of 1000r/min Mix 3 minutes, obtain mixed liquor G1；
(23) 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 65 DEG C after the washing with alcohol that 100mL mass percent concentration is 92% Place 110 minutes in dry case, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P 2；
(24) 1.8mL tetraethyl orthosilicate and 12mL acetylacetone,2,4-pentanedione are added in mixed liquor F2, stir under the conditions of 1000r/min Mix 3 minutes, obtain mixed liquor G2；
(25) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P 4；
(26) 2.1mL tetraethyl orthosilicate and 15mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, stir under the conditions of 1000r/min Mix 3 minutes, obtain mixed liquor G3；
(27) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P 6；
(28) 2.4mL tetraethyl orthosilicate and 18mL acetylacetone,2,4-pentanedione are added in mixed liquor F4, stir under the conditions of 1000r/min Mix 3 minutes, obtain mixed liquor G4；
(29) Substance P 6 is added in mixed liquor G4, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature It is filtered to remove liquid and obtains Substance P 7, Substance P 7 is after the washing with alcohol that 100mL mass percent concentration is 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain Substance P；
(30) by 6.33 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；
(31) MgCl for 0.46mol/L by 30mL molar concentration2Solution and 70mL molar concentration are the InCl of 0.91mol/L3Molten Liquid is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(32) 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 65 DEG C after the washing with alcohol that 100mL mass percent concentration is 92% Place 110 minutes in dry case, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q2；
(33) MgCl for 0.56mol/L by 40mL molar concentration2Solution and 60mL molar concentration are the InCl of 0.71mol/L3Molten Liquid is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(34) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q4；
(35) MgCl for 0.66mol/L by 50mL molar concentration2Solution and 50mL molar concentration are the InCl of 0.51mol/L3Molten Liquid is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(36) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q6；
(37) MgCl for 0.76mol/L by 60mL molar concentration2Solution and 40mL molar concentration are the InCl of 0.31mol/L3Molten Liquid is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(38) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material Q；
(39) by 26.34 grams of PbCl2With 9.54 grams of BiCl3It is added in 800mL deionized water, stir under the conditions of 1000r/min 10 minutes, after shaking up, it is divided into 4 parts of equivalent, obtain mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4；
(40) by 11.28 grams of NaOH and 7.63 gram of Na2CO3It is added in 800mL deionized water, stir under the conditions of 1000r/min 10 minutes, after shaking up, it is divided into 4 parts of equivalent, obtain mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4；
(41) 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；
(42) CdCl for 0.25mol/L by 40mL molar concentration2Solution is added in mixed liquor Y1, under the conditions of 1000r/min Stirring 3 minutes, obtains mixed liquor Z1；
(43) 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 65 DEG C after the washing with alcohol that 100mL mass percent concentration is 92% Place 110 minutes in dry case, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material R2；
(44) 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；
(45) CdCl for 0.45mol/L by 50mL molar concentration2Solution is added in mixed liquor Y2, under the conditions of 1000r/min Stirring 3 minutes, obtains mixed liquor Z2；
(46) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material R4；
(47) 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；
(48) CdCl for 0.65mol/L by 60mL molar concentration2Solution is added in mixed liquor Y3, under the conditions of 1000r/min Stirring 3 minutes, obtains mixed liquor Z3；
(49) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, obtain material R6；
(50) 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；
(51) CdCl for 0.85mol/L by 70mL molar concentration2Solution is added in mixed liquor Y4, under the conditions of 1000r/min Stirring 3 minutes, obtains mixed liquor Z4；
(52) 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 92% at 65 DEG C Place 110 minutes in drying baker, be subsequently placed in Muffle furnace roasting 60 minutes under the conditions of 490 DEG C, the material obtaining is to be used Remove the support type foam Al catalysts of dimethylformamide in supercritical water oxidation.
CN201610899815.7A 2016-10-14 2016-10-14 Load-type foamed aluminum catalyst for removing dimethyl formamide by use of supercritical water oxidization Pending CN106423210A (en)

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