CN106268863A - The support type ferroso-ferric oxide catalyst of DCBP is removed for supercritical water oxidation - Google Patents

The support type ferroso-ferric oxide catalyst of DCBP is removed for supercritical water oxidation Download PDF

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CN106268863A
CN106268863A CN201610899088.4A CN201610899088A CN106268863A CN 106268863 A CN106268863 A CN 106268863A CN 201610899088 A CN201610899088 A CN 201610899088A CN 106268863 A CN106268863 A CN 106268863A
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mixed liquor
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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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    • 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
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
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  • Environmental & Geological Engineering (AREA)
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Abstract

The invention discloses the support type ferroso-ferric oxide catalyst removing DCBP for supercritical water oxidation.Through AgNO after ferroso-ferric oxide cleaning3Modified it is prepared as material M；Material M is prepared as material N by the mixed liquor polyvinylpyrrolidone, methanol, three rhodium trichloride hydrates, three hydrate ruthenium trichlorides, concentrated hydrochloric acid, sodium borohydride prepared is modified；Material N is by by ZnCl2、PbCl2, the mixed liquor prepared of concentrated nitric acid, carbamide, ammonium fluoride is modified is prepared as material O；Material O is prepared as Substance P by the mixed liquor positive for metatitanic acid four fourth fat, tetraethyl orthosilicate, acetylacetone,2,4-pentanedione prepared is modified；Substance P is by by ZrCl4、CdCl2、CeCl3The mixed liquor of preparation is modified is prepared as material Q；Material Q is by by SrCl2、SbCl3、NaOH、Na2CO3、MgCl2The modified material obtained of mixed liquor of preparation is the support type ferroso-ferric oxide catalyst removing DCBP for supercritical water oxidation.

Description

The support type ferroso-ferric oxide catalyst of DCBP is removed for supercritical water oxidation
Technical field
The invention belongs to the supercritical Water Oxidation Technology field that organic wastewater with difficult degradation thereby processes, be used for surpassing particularly to one The support type ferroso-ferric oxide catalyst of critical oxidation removal DCBP.
Background technology
Supercritical water oxidation is a kind of wastewater processing technology grown up the eighties in 20th century, mainly utilize molecular oxygen or Hydrogen peroxide is as oxidant, using supercritical water as solvent, oxidation Decomposition organic pollution.Due to supercritical in oxidizing process Water is to various Organic substances and the good dissolubility of oxygen, and Organic substance, oxidant and supercritical water form homogeneous phase, and reaction is not Meeting restriction hindered because of alternate mass transfer, reaction rate can be greatly improved.Supercritical water oxidation treatment technology anti- Answering temperature to be generally 400～600 DEG C, pressure is 30～50MPa, and the organic carbon in organic pollution changes into carbon dioxide, hydrogen Changing into water, halogen atom changes into the ion of halogenide, sulfur and phosphorus and changes into sulfate and phosphate respectively, and organic nitrogen converts Becoming nitrogen, these products are nontoxic product.Therefore, supercritical Water Oxidation Technology has clearance height, reacts thorough, place Manage the advantages such as effective, non-secondary pollution.
Although supercritical Water Oxidation Technology is an emerging pollutant treatment technology with broad prospect of application, but it is high The harsh reaction condition of temperature high pressure is the highest with the requirement of management level to running.Therefore, in order to accelerate reaction rate, reduce instead Between Ying Shi, reducing reaction temperature, make supercritical Water Oxidation Technology can give full play of the advantage of self, many researcheres will catalysis Agent introduces supercritical Water Oxidation Technology, develops catalytic supercritical water oxidation technology.Catalytic supercritical water oxidation technology is commonly used Catalyst be MnO2、CuO、TiO2、CeO2、Al2O3, Pt or the most several material composition composite catalyst such as Cr2O3/ Al2O3、CuO/A12O3、MnO2/CeO2Deng, but these catalyst existence and stabilities can poor, the shortcoming such as catalysis activity is relatively low, Limit catalytic supercritical water oxidation technology water process in popularization and application and development, so the research of new catalytic material with Preparation also needs to strengthen further, also lacks the catalyst removing DCBP for supercritical water oxidation particularly at present.
Summary of the invention
It is an object of the invention to provide a kind of support type ferroso-ferric oxide removing DCBP for supercritical water oxidation Catalyst, specifically comprising the following steps that of its preparation method
(1) 500mL third is put into by after 83g ferriferrous oxide particles 300mL deionized water wash that particle diameter is 4～6mm Soaking 1h in ketone, after filtration, removing liquid obtains material M0, material M0 and obtains material M1 after 300mL deionized water wash, will Material M1 puts into immersion 0.5h in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L, removes liquid and obtain thing after filtration Matter M2, material M2 300mL deionized water wash, then with after the washing with alcohol that 500mL mass percent concentration is 95% 85 DEG C drying baker in place 1.5h, obtain material M3, material M3 joined the AgNO that 250mL molar concentration is 2.07mol/L3 In solution, shake 75 minutes in the shaking table that temperature is 65 DEG C, be filtered to remove liquid after being cooled to room temperature and obtain material M4, material M4 places 140 minutes after the washing with alcohol that 100mL mass percent concentration is 97% in the drying baker of 76 DEG C, is subsequently placed in In Muffle furnace under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 1.99 grams of polyvinylpyrrolidones and the methanol solution that 650mL mass percent concentration is 80% are joined Volume is in 1000mL conical flask, stirs 10 minutes, be divided into equivalent 5 parts, 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) 1.68 gram of three rhodium trichloride hydrate, 2.66 gram of three hydrate ruthenium trichloride and 850mL deionized water are joined appearance Amass as in 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into equivalent 5 parts, obtain mixed liquid B 1, Mixed liquid B 2, mixed liquid B 3, mixed liquid B 4, mixed liquid B 5；
(4) formalin that thing mixed liquor A 1 and 26mL mass percent concentration is 37% is joined in mixed liquid B 1, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(5) material M is joined in mixed liquor C1, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material N1, material N1 after the washing with alcohol that 100mL mass percent concentration is 97% at 76 DEG C Drying baker in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material N2；
(6) formalin that thing mixed liquor A 2 and 23mL mass percent concentration is 37% is joined in mixed liquid B 2, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(7) material N2 is joined in mixed liquor C2, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material N3, material N3 after the washing with alcohol that 100mL mass percent concentration is 97% at 76 DEG C Drying baker in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material N4；
(8) formalin that thing mixed liquor A 3 and 20mL mass percent concentration is 37% is joined in mixed liquid B 3, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(9) material N4 is joined in mixed liquor C3, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material N5, material N5 after the washing with alcohol that 100mL mass percent concentration is 97% at 76 DEG C Drying baker in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material N6；
(10) formalin that thing mixed liquor A 4 and 17mL mass percent concentration is 37% is joined in mixed liquid B 4, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C4；
(11) material N6 is joined in mixed liquor C4, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material N7, material N7 after the washing with alcohol that 100mL mass percent concentration is 97% 76 DEG C drying baker in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material N8；
(12) formalin that thing mixed liquor A 5 and 14mL mass percent concentration is 37% is joined in mixed liquid B 5, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C5；
(13) material N8 is joined in mixed liquor C5, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material N9, material N9 after the washing with alcohol that 100mL mass percent concentration is 97% 76 DEG C drying baker in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material N；
(14) by 5.24 grams of ZnCl2With 7.58 grams of CdCl2Join in 800mL ethanol, under the conditions of 1000r/min, stir 3 Minute, add 5mL concentrated nitric acid, be divided into equivalent 4 parts after shaking up, obtain mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4；
(15) 1.68 grams of carbamide and 0.42 gram of ammonium fluoride are joined in mixed liquor D1, under the conditions of 1000r/min, stir 3 Minute, obtain mixed liquor E1；
(16) material N is joined in mixed liquor E1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material O1, material O1 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material O2；
(17) 1.63 grams of carbamide and 0.40 gram of ammonium fluoride are joined in mixed liquor D2, under the conditions of 1000r/min, stir 3 Minute, obtain mixed liquor E2；
(18) material O2 is joined in mixed liquor E2, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material O3, material O3 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material O4；
(19) 1.58 grams of carbamide and 0.38 gram of ammonium fluoride are joined in mixed liquor D3, under the conditions of 1000r/min, stir 3 Minute, obtain mixed liquor E3；
(20) material O4 is joined in mixed liquor E3, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material O5, material O5 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material O6；
(21) 1.53 grams of carbamide and 0.36 gram of ammonium fluoride are joined in mixed liquor D4, under the conditions of 1000r/min, stir 3 Minute, obtain mixed liquor E4；
(22) material O6 is joined in mixed liquor E4, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material O7, material O7 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material O；
(23) positive for 4.29 grams of metatitanic acids four fourth fat is being joined in 800mL dehydrated alcohol under 1000r/min stirring condition, Under the conditions of 1000r/min stir 5 minutes, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into equivalent 4 parts, obtain mixed liquor F1, Mixed liquor F2, mixed liquor F3, mixed liquor F4；
(24) 2.9mL tetraethyl orthosilicate and 18mL acetylacetone,2,4-pentanedione are joined in mixed liquor F1, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G1；
(25) material O is joined in mixed liquor G1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain Substance P 1, Substance P 1 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain Substance P 2；
(26) 2.7mL tetraethyl orthosilicate and 19mL acetylacetone,2,4-pentanedione are joined in mixed liquor F2, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G2；
(27) Substance P 2 is joined in mixed liquor G2, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room Be filtered to remove liquid after temperature and obtain Substance P 3, Substance P 3 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain Substance P 4；
(28) 2.5mL tetraethyl orthosilicate and 20mL acetylacetone,2,4-pentanedione are joined in mixed liquor F3, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G3；
(29) Substance P 4 is joined in mixed liquor G3, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room Be filtered to remove liquid after temperature and obtain Substance P 5, Substance P 5 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain Substance P 6；
(30) 2.3mL tetraethyl orthosilicate and 21mL acetylacetone,2,4-pentanedione are joined in mixed liquor F4, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G4；
(31) Substance P 6 is joined in mixed liquor G4, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room Be filtered to remove liquid after temperature and obtain Substance P 7, Substance P 7 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain Substance P；
(32) by 6.34 grams of ZrCl4Volume is joined with the sodium citrate solution that 800mL mass percent concentration is 10% For in 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into equivalent 4 parts, obtain mixed liquor H1, mix Close liquid H2, mixed liquor H3, mixed liquor H4；
(33) it is the CdCl of 0.47mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.91mol/L's CeCl3Solution joins in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(34) Substance P is joined in mixed liquor J1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material Q1, material Q1 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material Q2；
(35) it is the CdCl of 0.57mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.71mol/L's CeCl3Solution joins in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(36) material Q2 is joined in mixed liquor J2, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material Q3, material Q3 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material Q4；
(37) it is the CdCl of 0.67mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.51mol/L's CeCl3Solution joins in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(38) material Q4 is joined in mixed liquor J3, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material Q5, material Q5 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material Q6；
(39) it is the CdCl of 0.77mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.31mol/L's CeCl3Solution joins in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(40) material Q6 is joined in mixed liquor J4, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material Q7, material Q7 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material Q；
(41) by 22.34 grams of SrCl2With 7.26 grams of SbCl3Join in 800mL deionized water, under the conditions of 1000r/min Stir 10 minutes, after shaking up, be divided into equivalent 5 parts, obtain mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4, mixed liquor K5；
(42) by 11.28 grams of NaOH and 7.63 grams of Na2CO3Join in 800mL deionized water, under the conditions of 1000r/min Stir 10 minutes, after shaking up, be divided into equivalent 5 parts, obtain mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4, mixed liquor L5；
(43) 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 the pH value of mixed liquor X1 is adjusted to 9.5～ 10.0, obtain mixed liquor Y1；
(44) it is the MgCl of 0.53mol/L by 40mL molar concentration2Solution joins in mixed liquor Y1, at 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Z1；
(45) material Q is joined in mixed liquor Z1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material R1, material R1 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material R2；
(46) 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 the pH value of mixed liquor X2 is adjusted to 9.5～ 10.0, obtain mixed liquor Y2；
(47) it is the MgCl of 0.63mol/L by 50mL molar concentration2Solution joins in mixed liquor Y2, at 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Z2；
(48) material R2 is joined in mixed liquor Z2, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material R3, material R3 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material R4；
(49) 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 the pH value of mixed liquor X3 is adjusted to 9.5～ 10.0, obtain mixed liquor Y3；
(50) it is the MgCl of 0.73mol/L by 60mL molar concentration2Solution joins in mixed liquor Y3, at 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Z3；
(51) material R4 is joined in mixed liquor Z3, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material R5, material R5 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material R6；
(52) 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 the pH value of mixed liquor X4 is adjusted to 9.5～ 10.0, obtain mixed liquor Y4；
(53) it is the MgCl of 0.83mol/L by 70mL molar concentration2Solution joins in mixed liquor Y4, at 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Z4；
(54) material R6 is joined in mixed liquor Z4, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material R7, material R7 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material R8；
(55) 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 the pH value of mixed liquor X5 is adjusted to 9.5～ 10.0, obtain mixed liquor Y5；
(56) it is the MgCl of 0.93mol/L by 80mL molar concentration2Solution joins in mixed liquor Y5, at 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Z5；
(57) material R8 is joined in mixed liquor Z5, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material R9, material R9 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, the material obtained is i.e. For removing the support type ferroso-ferric oxide catalyst of DCBP for supercritical water oxidation.
The invention has the beneficial effects as follows, the support type four for supercritical water oxidation removal DCBP prepared aoxidizes three Iron catalyst has that stability is strong, activity height, life-span length, to DCBP removal efficiency high.
Detailed description of the invention
The present invention provides a kind of support type ferroso-ferric oxide catalyst removing DCBP for supercritical water oxidation, under Face illustrates in fact to execute process by an example.
Embodiment 1.
(1) 500mL third is put into by after 83g ferriferrous oxide particles 300mL deionized water wash that particle diameter is 4～6mm Soaking 1h in ketone, after filtration, removing liquid obtains material M0, material M0 and obtains material M1 after 300mL deionized water wash, will Material M1 puts into immersion 0.5h in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L, removes liquid and obtain thing after filtration Matter M2, material M2 300mL deionized water wash, then with after the washing with alcohol that 500mL mass percent concentration is 95% 85 DEG C drying baker in place 1.5h, obtain material M3, material M3 joined the AgNO that 250mL molar concentration is 2.07mol/L3 In solution, shake 75 minutes in the shaking table that temperature is 65 DEG C, be filtered to remove liquid after being cooled to room temperature and obtain material M4, material M4 places 140 minutes after the washing with alcohol that 100mL mass percent concentration is 97% in the drying baker of 76 DEG C, is subsequently placed in In Muffle furnace under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 1.99 grams of polyvinylpyrrolidones and the methanol solution that 650mL mass percent concentration is 80% are joined Volume is in 1000mL conical flask, stirs 10 minutes, be divided into equivalent 5 parts, 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) 1.68 gram of three rhodium trichloride hydrate, 2.66 gram of three hydrate ruthenium trichloride and 850mL deionized water are joined appearance Amass as in 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into equivalent 5 parts, obtain mixed liquid B 1, Mixed liquid B 2, mixed liquid B 3, mixed liquid B 4, mixed liquid B 5；
(4) formalin that thing mixed liquor A 1 and 26mL mass percent concentration is 37% is joined in mixed liquid B 1, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(5) material M is joined in mixed liquor C1, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material N1, material N1 after the washing with alcohol that 100mL mass percent concentration is 97% at 76 DEG C Drying baker in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material N2；
(6) formalin that thing mixed liquor A 2 and 23mL mass percent concentration is 37% is joined in mixed liquid B 2, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(7) material N2 is joined in mixed liquor C2, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material N3, material N3 after the washing with alcohol that 100mL mass percent concentration is 97% at 76 DEG C Drying baker in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material N4；
(8) formalin that thing mixed liquor A 3 and 20mL mass percent concentration is 37% is joined in mixed liquid B 3, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(9) material N4 is joined in mixed liquor C3, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material N5, material N5 after the washing with alcohol that 100mL mass percent concentration is 97% at 76 DEG C Drying baker in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material N6；
(10) formalin that thing mixed liquor A 4 and 17mL mass percent concentration is 37% is joined in mixed liquid B 4, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C4；
(11) material N6 is joined in mixed liquor C4, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material N7, material N7 after the washing with alcohol that 100mL mass percent concentration is 97% 76 DEG C drying baker in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material N8；
(12) formalin that thing mixed liquor A 5 and 14mL mass percent concentration is 37% is joined in mixed liquid B 5, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C5；
(13) material N8 is joined in mixed liquor C5, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material N9, material N9 after the washing with alcohol that 100mL mass percent concentration is 97% 76 DEG C drying baker in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material N；
(14) by 5.24 grams of ZnCl2With 7.58 grams of CdCl2Join in 800mL ethanol, under the conditions of 1000r/min, stir 3 Minute, add 5mL concentrated nitric acid, be divided into equivalent 4 parts after shaking up, obtain mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4；
(15) 1.68 grams of carbamide and 0.42 gram of ammonium fluoride are joined in mixed liquor D1, under the conditions of 1000r/min, stir 3 Minute, obtain mixed liquor E1；
(16) material N is joined in mixed liquor E1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material O1, material O1 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material O2；
(17) 1.63 grams of carbamide and 0.40 gram of ammonium fluoride are joined in mixed liquor D2, under the conditions of 1000r/min, stir 3 Minute, obtain mixed liquor E2；
(18) material O2 is joined in mixed liquor E2, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material O3, material O3 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material O4；
(19) 1.58 grams of carbamide and 0.38 gram of ammonium fluoride are joined in mixed liquor D3, under the conditions of 1000r/min, stir 3 Minute, obtain mixed liquor E3；
(20) material O4 is joined in mixed liquor E3, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material O5, material O5 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material O6；
(21) 1.53 grams of carbamide and 0.36 gram of ammonium fluoride are joined in mixed liquor D4, under the conditions of 1000r/min, stir 3 Minute, obtain mixed liquor E4；
(22) material O6 is joined in mixed liquor E4, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material O7, material O7 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material O；
(23) positive for 4.29 grams of metatitanic acids four fourth fat is being joined in 800mL dehydrated alcohol under 1000r/min stirring condition, Under the conditions of 1000r/min stir 5 minutes, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into equivalent 4 parts, obtain mixed liquor F1, Mixed liquor F2, mixed liquor F3, mixed liquor F4；
(24) 2.9mL tetraethyl orthosilicate and 18mL acetylacetone,2,4-pentanedione are joined in mixed liquor F1, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G1；
(25) material O is joined in mixed liquor G1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain Substance P 1, Substance P 1 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain Substance P 2；
(26) 2.7mL tetraethyl orthosilicate and 19mL acetylacetone,2,4-pentanedione are joined in mixed liquor F2, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G2；
(27) Substance P 2 is joined in mixed liquor G2, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room Be filtered to remove liquid after temperature and obtain Substance P 3, Substance P 3 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain Substance P 4；
(28) 2.5mL tetraethyl orthosilicate and 20mL acetylacetone,2,4-pentanedione are joined in mixed liquor F3, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G3；
(29) Substance P 4 is joined in mixed liquor G3, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room Be filtered to remove liquid after temperature and obtain Substance P 5, Substance P 5 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain Substance P 6；
(30) 2.3mL tetraethyl orthosilicate and 21mL acetylacetone,2,4-pentanedione are joined in mixed liquor F4, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor G4；
(31) Substance P 6 is joined in mixed liquor G4, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room Be filtered to remove liquid after temperature and obtain Substance P 7, Substance P 7 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain Substance P；
(32) by 6.34 grams of ZrCl4Volume is joined with the sodium citrate solution that 800mL mass percent concentration is 10% For in 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into equivalent 4 parts, obtain mixed liquor H1, mix Close liquid H2, mixed liquor H3, mixed liquor H4；
(33) it is the CdCl of 0.47mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.91mol/L's CeCl3Solution joins in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(34) Substance P is joined in mixed liquor J1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material Q1, material Q1 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material Q2；
(35) it is the CdCl of 0.57mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.71mol/L's CeCl3Solution joins in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(36) material Q2 is joined in mixed liquor J2, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material Q3, material Q3 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material Q4；
(37) it is the CdCl of 0.67mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.51mol/L's CeCl3Solution joins in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(38) material Q4 is joined in mixed liquor J3, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material Q5, material Q5 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material Q6；
(39) it is the CdCl of 0.77mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.31mol/L's CeCl3Solution joins in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(40) material Q6 is joined in mixed liquor J4, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material Q7, material Q7 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material Q；
(41) by 22.34 grams of SrCl2With 7.26 grams of SbCl3Join in 800mL deionized water, under the conditions of 1000r/min Stir 10 minutes, after shaking up, be divided into equivalent 5 parts, obtain mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4, mixed liquor K5；
(42) by 11.28 grams of NaOH and 7.63 grams of Na2CO3Join in 800mL deionized water, under the conditions of 1000r/min Stir 10 minutes, after shaking up, be divided into equivalent 5 parts, obtain mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4, mixed liquor L5；
(43) 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 the pH value of mixed liquor X1 is adjusted to 9.5～ 10.0, obtain mixed liquor Y1；
(44) it is the MgCl of 0.53mol/L by 40mL molar concentration2Solution joins in mixed liquor Y1, at 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Z1；
(45) material Q is joined in mixed liquor Z1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room temperature After be filtered to remove liquid and obtain material R1, material R1 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material R2；
(46) 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 the pH value of mixed liquor X2 is adjusted to 9.5～ 10.0, obtain mixed liquor Y2；
(47) it is the MgCl of 0.63mol/L by 50mL molar concentration2Solution joins in mixed liquor Y2, at 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Z2；
(48) material R2 is joined in mixed liquor Z2, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material R3, material R3 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material R4；
(49) 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 the pH value of mixed liquor X3 is adjusted to 9.5～ 10.0, obtain mixed liquor Y3；
(50) it is the MgCl of 0.73mol/L by 60mL molar concentration2Solution joins in mixed liquor Y3, at 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Z3；
(51) material R4 is joined in mixed liquor Z3, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material R5, material R5 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material R6；
(52) 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 the pH value of mixed liquor X4 is adjusted to 9.5～ 10.0, obtain mixed liquor Y4；
(53) it is the MgCl of 0.83mol/L by 70mL molar concentration2Solution joins in mixed liquor Y4, at 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Z4；
(54) material R6 is joined in mixed liquor Z4, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material R7, material R7 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtain material R8；
(55) 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 the pH value of mixed liquor X5 is adjusted to 9.5～ 10.0, obtain mixed liquor Y5；
(56) it is the MgCl of 0.93mol/L by 80mL molar concentration2Solution joins in mixed liquor Y5, at 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Z5；
(57) material R8 is joined in mixed liquor Z5, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to room It is filtered to remove liquid after temperature and obtains material R9, material R9 after the washing with alcohol that 100mL mass percent concentration is 97% 72 DEG C drying baker in place 135 minutes, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, the material obtained is i.e. For removing the support type ferroso-ferric oxide catalyst of DCBP for supercritical water oxidation.
Support type four oxidation of for supercritical water oxidation removing DCBP of using the inventive method prepare is presented herein below Three iron catalysts have carried out oxidative degradation test to the waste water containing DCBP in afterflow fixed bed supercritical reaction device, enter The one step explanation present invention.
Support type ferroso-ferric oxide Catalyst packing the inventive method prepared is anti-at continuous current flow fixed bed supercritical water Answering in device, the waste water containing DCBP has been carried out Degrading experiment, result shows that being filled with this support type ferroso-ferric oxide urges The DCBP in waste water can efficiently be removed by the continuous current flow fixed bed supercritical water reaction device of agent, when the dichloro in waste water joins When benzene concentration is 22.7mg/L, being 355 DEG C in temperature, pressure is 25MPa, and the time of staying is under the reaction condition of 35 seconds, processes DCBP concentration in rear water outlet is reduced to 4.7mg/L.

Claims (1)

1. the support type ferroso-ferric oxide catalyst removing DCBP for supercritical water oxidation, it is characterised in that system Specifically comprising the following steps that of this catalyst method standby
(1) put into after 83g ferriferrous oxide particles 300mL deionized water wash that particle diameter is 4～6mm in 500mL acetone Soaking 1h, after filtration, removing liquid obtains material M0, material M0 and obtains material M1 after 300mL deionized water wash, by material M1 puts into immersion 0.5h in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L, removes liquid and obtain material M2 after filtration, Material M2 300mL deionized water wash, then by dry at 85 DEG C after the washing with alcohol that 500mL mass percent concentration is 95% Dry case is placed 1.5h, obtains material M3, material M3 is joined the AgNO that 250mL molar concentration is 2.07mol/L3Solution In, shake 75 minutes in the shaking table that temperature is 65 DEG C, 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 the drying baker of 76 DEG C place 140 minutes, be subsequently placed in Muffle In stove under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 1.99 grams of polyvinylpyrrolidones and the methanol solution that 650mL mass percent concentration is 80% are joined volume For in 1000mL conical flask, stir 10 minutes under the conditions of 1000r/min, after shaking up, be divided into equivalent 5 parts, obtain mixed liquor A 1, Mixed liquor A 2, mixed liquor A 3, mixed liquor A 4, mixed liquor A 5；
(3) 1.68 gram of three rhodium trichloride hydrate, 2.66 gram of three hydrate ruthenium trichloride and 850mL deionized water being joined volume is In 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into equivalent 5 parts, obtain mixed liquid B 1, mixing Liquid B2, mixed liquid B 3, mixed liquid B 4, mixed liquid B 5；
(4) formalin that thing mixed liquor A 1 and 26mL mass percent concentration is 37% is joined in mixed liquid B 1, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(5) material M is joined in mixed liquor C1, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature Filter liquid and obtain material N1, material N1 dry at 76 DEG C after the washing with alcohol that 100mL mass percent concentration is 97% Dry case is placed 141 minutes, is subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtains material N2；
(6) formalin that thing mixed liquor A 2 and 23mL mass percent concentration is 37% is joined in mixed liquid B 2, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(7) material N2 is joined in mixed liquor C2, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature Filter liquid and obtain material N3, material N3 dry at 76 DEG C after the washing with alcohol that 100mL mass percent concentration is 97% Dry case is placed 141 minutes, is subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtains material N4；
(8) formalin that thing mixed liquor A 3 and 20mL mass percent concentration is 37% is joined in mixed liquid B 3, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(9) material N4 is joined in mixed liquor C3, shake 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature Filter liquid and obtain material N5, material N5 dry at 76 DEG C after the washing with alcohol that 100mL mass percent concentration is 97% Dry case is placed 141 minutes, is subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtains material N6；
(10) formalin that thing mixed liquor A 4 and 17mL mass percent concentration is 37% is joined in mixed liquid B 4, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C4；
(11) material N6 is joined in mixed liquor C4, shake 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material N7, material N7 after the washing with alcohol that 100mL mass percent concentration is 97% at 76 DEG C Drying baker is placed 141 minutes, is subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtains material N8；
(12) formalin that thing mixed liquor A 5 and 14mL mass percent concentration is 37% is joined in mixed liquid B 5, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C5；
(13) material N8 is joined in mixed liquor C5, shake 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material N9, material N9 after the washing with alcohol that 100mL mass percent concentration is 97% at 76 DEG C Drying baker is placed 141 minutes, is subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtains material N；
(14) by 5.24 grams of ZnCl2With 7.58 grams of CdCl2Join in 800mL ethanol, under the conditions of 1000r/min, stir 3 points Clock, adds 5mL concentrated nitric acid, is divided into equivalent 4 parts, obtains mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4 after shaking up；
(15) 1.68 grams of carbamide and 0.42 gram of ammonium fluoride are joined in mixed liquor D1, under the conditions of 1000r/min, stir 3 points Clock, obtains mixed liquor E1；
(16) material N is joined in mixed liquor E1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to mistake after room temperature Filter liquid and obtain material O1, material O1 dry at 72 DEG C after the washing with alcohol that 100mL mass percent concentration is 97% Dry case is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material O2；
(17) 1.63 grams of carbamide and 0.40 gram of ammonium fluoride are joined in mixed liquor D2, under the conditions of 1000r/min, stir 3 points Clock, obtains mixed liquor E2；
(18) material O2 is joined in mixed liquor E2, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material O3, material O3 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material O4；
(19) 1.58 grams of carbamide and 0.38 gram of ammonium fluoride are joined in mixed liquor D3, under the conditions of 1000r/min, stir 3 points Clock, obtains mixed liquor E3；
(20) material O4 is joined in mixed liquor E3, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material O5, material O5 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material O6；
(21) 1.53 grams of carbamide and 0.36 gram of ammonium fluoride are joined in mixed liquor D4, under the conditions of 1000r/min, stir 3 points Clock, obtains mixed liquor E4；
(22) material O6 is joined in mixed liquor E4, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material O7, material O7 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material O；
(23) positive for 4.29 grams of metatitanic acids four fourth fat is being joined in 800mL dehydrated alcohol under 1000r/min stirring condition, Stir 5 minutes under the conditions of 1000r/min, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into equivalent 4 parts, obtain mixed liquor F1, mix Close liquid F2, mixed liquor F3, mixed liquor F4；
(24) 2.9mL tetraethyl orthosilicate and 18mL acetylacetone,2,4-pentanedione are joined in mixed liquor F1, stir under the conditions of 1000r/min Mix 3 minutes, obtain mixed liquor G1；
(25) material O is joined in mixed liquor G1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to mistake after room temperature Filter liquid and obtain Substance P 1, Substance P 1 dry at 72 DEG C after the washing with alcohol that 100mL mass percent concentration is 97% Dry case is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains Substance P 2；
(26) 2.7mL tetraethyl orthosilicate and 19mL acetylacetone,2,4-pentanedione are joined in mixed liquor F2, stir under the conditions of 1000r/min Mix 3 minutes, obtain mixed liquor G2；
(27) Substance P 2 is joined in mixed liquor G2, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature Be filtered to remove liquid and obtain Substance P 3, Substance P 3 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains Substance P 4；
(28) 2.5mL tetraethyl orthosilicate and 20mL acetylacetone,2,4-pentanedione are joined in mixed liquor F3, stir under the conditions of 1000r/min Mix 3 minutes, obtain mixed liquor G3；
(29) Substance P 4 is joined in mixed liquor G3, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature Be filtered to remove liquid and obtain Substance P 5, Substance P 5 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains Substance P 6；
(30) 2.3mL tetraethyl orthosilicate and 21mL acetylacetone,2,4-pentanedione are joined in mixed liquor F4, stir under the conditions of 1000r/min Mix 3 minutes, obtain mixed liquor G4；
(31) Substance P 6 is joined in mixed liquor G4, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature Be filtered to remove liquid and obtain Substance P 7, Substance P 7 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains Substance P；
(32) by 6.34 grams of ZrCl4Joining 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 equivalent 4 parts after shaking up, obtain mixed liquor H1, mixing Liquid H2, mixed liquor H3, mixed liquor H4；
(33) it is the CdCl of 0.47mol/L by 30mL molar concentration2Solution and 70mL molar concentration are the CeCl of 0.91mol/L3Molten Liquid joins in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(34) Substance P is joined in mixed liquor J1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to mistake after room temperature Filter liquid and obtain material Q1, material Q1 dry at 72 DEG C after the washing with alcohol that 100mL mass percent concentration is 97% Dry case is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material Q2；
(35) it is the CdCl of 0.57mol/L by 40mL molar concentration2Solution and 60mL molar concentration are the CeCl of 0.71mol/L3Molten Liquid joins in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(36) material Q2 is joined in mixed liquor J2, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material Q3, material Q3 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material Q4；
(37) it is the CdCl of 0.67mol/L by 50mL molar concentration2Solution and 50mL molar concentration are the CeCl of 0.51mol/L3Molten Liquid joins in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(38) material Q4 is joined in mixed liquor J3, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material Q5, material Q5 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material Q6；
(39) it is the CdCl of 0.77mol/L by 60mL molar concentration2Solution and 40mL molar concentration are the CeCl of 0.31mol/L3Molten Liquid joins in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(40) material Q6 is joined in mixed liquor J4, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material Q7, material Q7 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material Q；
(41) by 22.34 grams of SrCl2With 7.26 grams of SbCl3Join in 800mL deionized water, stir under the conditions of 1000r/min 10 minutes, after shaking up, it is divided into equivalent 5 parts, obtains mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4, mixed liquor K5；
(42) by 11.28 grams of NaOH and 7.63 grams of Na2CO3Join in 800mL deionized water, stir under the conditions of 1000r/min 10 minutes, after shaking up, it is divided into equivalent 5 parts, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4, mixed liquor L5；
(43) under 1000r/min stirring condition, mixed liquor L1 is added drop-wise in mixed liquor K1, obtains mixed liquor X1, dense with mole The pH value of mixed liquor X1 is adjusted to 9.5～10.0 for the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L by degree, To mixed liquor Y1；
(44) it is the MgCl of 0.53mol/L by 40mL molar concentration2Solution joins in mixed liquor Y1, under the conditions of 1000r/min Stir 3 minutes, obtain mixed liquor Z1；
(45) material Q is joined in mixed liquor Z1, shake 15 minutes in the shaking table that temperature is 48 DEG C, be cooled to mistake after room temperature Filter liquid and obtain material R1, material R1 dry at 72 DEG C after the washing with alcohol that 100mL mass percent concentration is 97% Dry case is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material R2；
(46) under 1000r/min stirring condition, mixed liquor L2 is added drop-wise in mixed liquor K2, obtains mixed liquor X2, dense with mole The pH value of mixed liquor X2 is adjusted to 9.5～10.0 for the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L by degree, To mixed liquor Y2；
(47) it is the MgCl of 0.63mol/L by 50mL molar concentration2Solution joins in mixed liquor Y2, under the conditions of 1000r/min Stir 3 minutes, obtain mixed liquor Z2；
(48) material R2 is joined in mixed liquor Z2, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material R3, material R3 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material R4；
(49) under 1000r/min stirring condition, mixed liquor L3 is added drop-wise in mixed liquor K3, obtains mixed liquor X3, dense with mole The pH value of mixed liquor X3 is adjusted to 9.5～10.0 for the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L by degree, To mixed liquor Y3；
(50) it is the MgCl of 0.73mol/L by 60mL molar concentration2Solution joins in mixed liquor Y3, under the conditions of 1000r/min Stir 3 minutes, obtain mixed liquor Z3；
(51) material R4 is joined in mixed liquor Z3, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material R5, material R5 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material R6；
(52) under 1000r/min stirring condition, mixed liquor L4 is added drop-wise in mixed liquor K4, obtains mixed liquor X4, dense with mole The pH value of mixed liquor X4 is adjusted to 9.5～10.0 for the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L by degree, To mixed liquor Y4；
(53) it is the MgCl of 0.83mol/L by 70mL molar concentration2Solution joins in mixed liquor Y4, under the conditions of 1000r/min Stir 3 minutes, obtain mixed liquor Z4；
(54) material R6 is joined in mixed liquor Z4, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material R7, material R7 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Drying baker is placed 135 minutes, is subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, obtains material R8；
(55) under 1000r/min stirring condition, mixed liquor L5 is added drop-wise in mixed liquor K5, obtains mixed liquor X5, dense with mole The pH value of mixed liquor X5 is adjusted to 9.5～10.0 for the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L by degree, To mixed liquor Y5；
(56) it is the MgCl of 0.93mol/L by 80mL molar concentration2Solution joins in mixed liquor Y5, under the conditions of 1000r/min Stir 3 minutes, obtain mixed liquor Z5；
(57) material R8 is joined in mixed liquor Z5, shake 15 minutes in the shaking table that temperature is 48 DEG C, after being cooled to room temperature It is filtered to remove liquid and obtains material R9, material R9 after the washing with alcohol that 100mL mass percent concentration is 97% at 72 DEG C Placing 135 minutes in drying baker, be subsequently placed in Muffle furnace roasting 85 minutes under the conditions of 485 DEG C, the material obtained is use The support type ferroso-ferric oxide catalyst of DCBP is removed in supercritical water oxidation.
CN201610899088.4A 2016-10-14 2016-10-14 The support type ferroso-ferric oxide catalyst of DCBP is removed for supercritical water oxidation Pending CN106268863A (en)

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