CN106423209A - Supported vanadium pentoxide catalyst used for removing dimethyl formamide through oxidation of supercritical water - Google Patents
Supported vanadium pentoxide catalyst used for removing dimethyl formamide through oxidation of supercritical water Download PDFInfo
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- CN106423209A CN106423209A CN201610899813.8A CN201610899813A CN106423209A CN 106423209 A CN106423209 A CN 106423209A CN 201610899813 A CN201610899813 A CN 201610899813A CN 106423209 A CN106423209 A CN 106423209A
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 title claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 230000003647 oxidation Effects 0.000 title abstract description 7
- 238000007254 oxidation reaction Methods 0.000 title abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 claims abstract description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 102100024304 Protachykinin-1 Human genes 0.000 claims abstract description 38
- 101800003906 Substance P Proteins 0.000 claims abstract description 38
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 5
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims abstract description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 4
- 239000011592 zinc chloride Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 225
- 238000003756 stirring Methods 0.000 claims description 96
- 239000007788 liquid Substances 0.000 claims description 92
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- 238000005406 washing Methods 0.000 claims description 63
- 238000001035 drying Methods 0.000 claims description 59
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000009284 supercritical water oxidation Methods 0.000 claims description 20
- 235000013877 carbamide Nutrition 0.000 claims description 15
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- 101710134784 Agnoprotein Proteins 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 abstract 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 abstract 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 229910001631 strontium chloride Inorganic materials 0.000 abstract 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 abstract 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract 1
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 abstract 1
- 235000005074 zinc chloride Nutrition 0.000 abstract 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- B01J23/898—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 vanadium, tantalum, niobium or polonium
-
- 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 supported vanadium pentoxide catalyst used for removing dimethyl formamide through oxidation of supercritical water. A substance M is prepared after vanadium pentoxide is cleaned and modified with AgNO3; a substance N is prepared after mixed liquor prepared from polyvinylpyrrolidone, methyl alcohol, palladium dichloride, rhodium chloride trihydrate, concentrated hydrochloric acid and sodium borohydride is modified with the substance M; a substance O is prepared after mixed liquor prepared from CuCl2, CdCl2, concentrated nitric acid, urea and ammonium fluoride is modified with the substance N; a substance P is prepared after mixed liquor prepared from tetra-n-butyl ester titanate, tetraethyl orthosilicate and acetylacetone is modified with the substance O; a substance Q is prepared after mixed liquor prepared from SnCl4, SrCl2 and BiCl3 is modified by the substance P; a substance, namely, the supported vanadium pentoxide catalyst used for removing dimethyl formamide through oxidation of supercritical water is prepared after mixed liquor prepared from ZnCl2, SbCl3, NaOH, Na2CO3 and NiCl2 is modified with the substance Q.
Description
Technical field
The invention belongs to the supercritical Water Oxidation Technology field that organic wastewater with difficult degradation thereby is processed, it is used for surpassing particularly to one kind
The support type vanadium pentoxide catalyst of critical oxidation removal 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 five removing dimethylformamide for supercritical water oxidation aoxidizes
Two vanadium catalysts, the comprising the following steps that of its preparation method：
(1) put into 500mL third after the 133g vanadium oxide particles 300mL deionized water wash being 4～6mm by particle diameter
Soak 1h in ketone, remove liquid after filtration and obtain material M0, material M0 obtains material M1 after 300mL deionized water wash, will
Material M1 puts in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L and soaks 0.5h, removes liquid and obtain thing after filtration
Matter M2,85 after material M2 300mL deionized water wash, then the washing with alcohol being 95% with 500mL mass percent concentration
DEG C drying baker in place 1.5h, obtain material M3, by material M3 be added to 250mL molar concentration be 2.67mol/L AgNO3
In solution, temperature be 65 DEG C shaking table in shake 75 minutes, be filtered to remove liquid after being cooled to room temperature and obtain material M4, material
M4 places 140 minutes after the washing with alcohol that 100mL mass percent concentration is 97% in 76 DEG C of drying baker, is subsequently placed in
In Muffle furnace under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 4.88 grams of Polyvinylpyrrolidone and methanol solution that 600mL mass percent concentration is 80% are added to
Volume is in 1000mL conical flask, stirs 10 minutes, be divided into 3 parts of equivalent, obtain mixed liquor after shaking up under the conditions of 1000r/min
A1, mixed liquor A 2, mixed liquor A 3；
(3) 0.6327 gram of palladium chloride and 180mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 in temperature
DEG C water-bath in shake 20 minutes, then place 140 minutes in 120 DEG C of drying baker, be cooled to after room temperature and add 200mL
Deionized water, under the conditions of 1000r/min stir 3 minutes, be divided into 3 parts of equivalent after shaking up, obtain mixed liquid B 1, mixed liquid B 2,
Mixed liquid B 3；
(4) 1.69 gram of three rhodium trichloride hydrate and 750mL deionized water being added to volume is in 1000mL conical flask,
Stir 3 minutes under the conditions of 1000r/min, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor A B1, mixed liquor A B2, mixed liquor A B3；
(5) sodium borohydride solution being 0.64mol/L by mixed liquor A 1, mixed liquor A B1 and 15mL molar concentration is added to
In mixed liquid B 1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(6) material M is added in mixed liquor C1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material N1, material N1 is after the washing with alcohol that 100mL mass percent concentration is 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；
(7) by mixed liquor A 2, mixed liquor A B2 and 13mL molar concentration be 054mol/L sodium borohydride solution be added to mixed
Close in liquid B2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(8) material N2 is added in mixed liquor C2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to 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；
(9) sodium borohydride solution being 0.44mol/L by mixed liquor A 3, mixed liquor A B3 and 11mL molar concentration is added to
In mixed liquid B 3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(10) material N4 is added in mixed liquor C3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material N5, material N5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(11) by 5.24 grams of CuCl2With 7.41 grams of CdCl2It is added in 850mL ethanol, stir 3 under the conditions of 1000r/min
Minute, add 5mL concentrated nitric acid, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4,
Mixed liquor D5；
(12) 4.39 grams of carbamide and 0.46 gram of ammonium fluoride are added in mixed liquor D1, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E1；
(13) material N is added in mixed liquor E1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material O1, material O1 is after the washing with alcohol that 100mL mass percent concentration is 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；
(14) 4.29 grams of carbamide and 0.44 gram of ammonium fluoride are added in mixed liquor D2, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E2；
(15) material O2 is added in mixed liquor E2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O3, material O3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(16) 4.19 grams of carbamide and 0.42 gram of ammonium fluoride are added in mixed liquor D3, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E3；
(17) material O4 is added in mixed liquor E3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O5, material O5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(18) 4.09 grams of carbamide and 0.40 gram of ammonium fluoride are added in mixed liquor D4, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E4；
(19) material O6 is added in mixed liquor E4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O7, material O7 is after the washing with alcohol that 100mL mass percent concentration is 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 O8；
(20) 3.99 grams of carbamide and 0.38 gram of ammonium fluoride are added in mixed liquor D5, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E5；
(21) material O8 is added in mixed liquor E5, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O9, material O9 is after the washing with alcohol that 100mL mass percent concentration is 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；
(22) by positive for 5.07 grams of metatitanic acids four fourth fat being added in 750mL dehydrated alcohol under 1000r/min stirring condition,
Under the conditions of 1000r/min stir 5 minutes, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor F1,
Mixed liquor F2, mixed liquor F3；
(23) 3.7mL tetraethyl orthosilicate and 13mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G1；
(24) material O is added in mixed liquor G1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain Substance P 1, Substance P 1 is after the 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；
(25) 3.5mL 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；
(26) Substance P 2 is added in mixed liquor G2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains Substance P 3, Substance P 3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(27) 3.3mL tetraethyl orthosilicate and 11mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G3；
(28) Substance P 4 is added in mixed liquor G3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains Substance P 5, Substance P 5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(29) by 6.35 grams of SnCl4It is added to volume with the sodium citrate solution that 800mL mass percent concentration is 10%
For, in 1000mL conical flask, stirring 3 minutes under the conditions of 1000r/min, being divided into 4 parts of equivalent after shaking up, obtain mixed liquor H1, mix
Close liquid H2, mixed liquor H3, mixed liquor H4；
(30) SrCl for 0.21mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.94mol/L's
BiCl3Solution is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(31) Substance P is added in mixed liquor J1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material Q1, material Q1 is after the washing with alcohol that 100mL mass percent concentration is 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；
(32) SrCl for 0.41mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.74mol/L's
BiCl3Solution is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(33) material Q2 is added in mixed liquor J2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q3, material Q3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(34) SrCl for 0.61mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.54mol/L's
BiCl3Solution is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(35) material Q4 is added in mixed liquor J3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q5, material Q5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(36) SrCl for 0.81mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.34mol/L's
BiCl3Solution is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(37) material Q6 is added in mixed liquor J4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q7, material Q7 is after the washing with alcohol that 100mL mass percent concentration is 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；
(38) by 26.75 grams of ZnCl2With 9.27 grams of SbCl3It 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；
(39) by 12.07 grams of NaOH and 7.46 gram of Na2CO3It is added in 800mL deionized water, under the conditions of 1000r/min
Stirring 10 minutes, is divided into 5 parts of equivalent, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4 after shaking up；
(40) under 1000r/min stirring condition, mixed liquor L1 is added drop-wise in mixed liquor K1, obtains mixed liquor X1, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X1～
10.0, obtain mixed liquor Y1；
(41) NiCl for 0.27mol/L by 40mL molar concentration2Solution is added in mixed liquor Y1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z1；
(42) material Q is added in mixed liquor Z1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material R1, material R1 is after the washing with alcohol that 100mL mass percent concentration is 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；
(43) under 1000r/min stirring condition, mixed liquor L2 is added drop-wise in mixed liquor K2, obtains mixed liquor X2, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X2～
10.0, obtain mixed liquor Y2；
(44) NiCl for 0.47mol/L by 50mL molar concentration2Solution is added in mixed liquor Y2, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z2；
(45) material R2 is added in mixed liquor Z2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R3, material R3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(46) under 1000r/min stirring condition, mixed liquor L3 is added drop-wise in mixed liquor K3, obtains mixed liquor X3, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X3～
10.0, obtain mixed liquor Y3；
(47) NiCl for 0.67mol/L by 60mL molar concentration2Solution is added in mixed liquor Y3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z3；
(48) material R4 is added in mixed liquor Z3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R5, material R5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(49) under 1000r/min stirring condition, mixed liquor L4 is added drop-wise in mixed liquor K4, obtains mixed liquor X4, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X4～
10.0, obtain mixed liquor Y4；
(50) NiCl for 0.87mol/L by 70mL molar concentration2Solution is added in mixed liquor Y4, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z4；
(51) material R6 is added in mixed liquor Z4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R7, material R7 is after the washing with alcohol that 100mL mass percent concentration is 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 vanadium pentoxide catalyst removing dimethylformamide for supercritical water oxidation.
The invention has the beneficial effects as follows, prepared support type five oxygen removing dimethylformamide for supercritical water oxidation
Change two vanadium catalysts and 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 vanadic anhydride catalysis removing dimethylformamide for supercritical water oxidation
Agent, to illustrate in fact to apply process below by an example.
Embodiment 1.
(1) put into 500mL third after the 133g vanadium oxide particles 300mL deionized water wash being 4～6mm by particle diameter
Soak 1h in ketone, remove liquid after filtration and obtain material M0, material M0 obtains material M1 after 300mL deionized water wash, will
Material M1 puts in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L and soaks 0.5h, removes liquid and obtain thing after filtration
Matter M2,85 after material M2 300mL deionized water wash, then the washing with alcohol being 95% with 500mL mass percent concentration
DEG C drying baker in place 1.5h, obtain material M3, by material M3 be added to 250mL molar concentration be 2.67mol/L AgNO3
In solution, temperature be 65 DEG C shaking table in shake 75 minutes, be filtered to remove liquid after being cooled to room temperature and obtain material M4, material
M4 places 140 minutes after the washing with alcohol that 100mL mass percent concentration is 97% in 76 DEG C of drying baker, is subsequently placed in
In Muffle furnace under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 4.88 grams of Polyvinylpyrrolidone and methanol solution that 600mL mass percent concentration is 80% are added to
Volume is in 1000mL conical flask, stirs 10 minutes, be divided into 3 parts of equivalent, obtain mixed liquor after shaking up under the conditions of 1000r/min
A1, mixed liquor A 2, mixed liquor A 3；
(3) 0.6327 gram of palladium chloride and 180mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 in temperature
DEG C water-bath in shake 20 minutes, then place 140 minutes in 120 DEG C of drying baker, be cooled to after room temperature and add 200mL
Deionized water, under the conditions of 1000r/min stir 3 minutes, be divided into 3 parts of equivalent after shaking up, obtain mixed liquid B 1, mixed liquid B 2,
Mixed liquid B 3；
(4) 1.69 gram of three rhodium trichloride hydrate and 750mL deionized water being added to volume is in 1000mL conical flask,
Stir 3 minutes under the conditions of 1000r/min, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor A B1, mixed liquor A B2, mixed liquor A B3；
(5) sodium borohydride solution being 0.64mol/L by mixed liquor A 1, mixed liquor A B1 and 15mL molar concentration is added to
In mixed liquid B 1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(6) material M is added in mixed liquor C1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material N1, material N1 is after the washing with alcohol that 100mL mass percent concentration is 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；
(7) by mixed liquor A 2, mixed liquor A B2 and 13mL molar concentration be 054mol/L sodium borohydride solution be added to mixed
Close in liquid B2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(8) material N2 is added in mixed liquor C2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to 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；
(9) sodium borohydride solution being 0.44mol/L by mixed liquor A 3, mixed liquor A B3 and 11mL molar concentration is added to
In mixed liquid B 3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(10) material N4 is added in mixed liquor C3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material N5, material N5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(11) by 5.24 grams of CuCl2With 7.41 grams of CdCl2It is added in 850mL ethanol, stir 3 under the conditions of 1000r/min
Minute, add 5mL concentrated nitric acid, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4,
Mixed liquor D5；
(12) 4.39 grams of carbamide and 0.46 gram of ammonium fluoride are added in mixed liquor D1, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E1；
(13) material N is added in mixed liquor E1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material O1, material O1 is after the washing with alcohol that 100mL mass percent concentration is 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；
(14) 4.29 grams of carbamide and 0.44 gram of ammonium fluoride are added in mixed liquor D2, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E2；
(15) material O2 is added in mixed liquor E2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O3, material O3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(16) 4.19 grams of carbamide and 0.42 gram of ammonium fluoride are added in mixed liquor D3, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E3；
(17) material O4 is added in mixed liquor E3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O5, material O5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(18) 4.09 grams of carbamide and 0.40 gram of ammonium fluoride are added in mixed liquor D4, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E4；
(19) material O6 is added in mixed liquor E4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O7, material O7 is after the washing with alcohol that 100mL mass percent concentration is 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 O8；
(20) 3.99 grams of carbamide and 0.38 gram of ammonium fluoride are added in mixed liquor D5, stir 3 under the conditions of 1000r/min
Minute, obtain mixed liquor E5；
(21) material O8 is added in mixed liquor E5, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material O9, material O9 is after the washing with alcohol that 100mL mass percent concentration is 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；
(22) by positive for 5.07 grams of metatitanic acids four fourth fat being added in 750mL dehydrated alcohol under 1000r/min stirring condition,
Under the conditions of 1000r/min stir 5 minutes, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor F1,
Mixed liquor F2, mixed liquor F3；
(23) 3.7mL tetraethyl orthosilicate and 13mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G1；
(24) material O is added in mixed liquor G1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain Substance P 1, Substance P 1 is after the 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；
(25) 3.5mL 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；
(26) Substance P 2 is added in mixed liquor G2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains Substance P 3, Substance P 3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(27) 3.3mL tetraethyl orthosilicate and 11mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor G3；
(28) Substance P 4 is added in mixed liquor G3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains Substance P 5, Substance P 5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(29) by 6.35 grams of SnCl4It is added to volume with the sodium citrate solution that 800mL mass percent concentration is 10%
For, in 1000mL conical flask, stirring 3 minutes under the conditions of 1000r/min, being divided into 4 parts of equivalent after shaking up, obtain mixed liquor H1, mix
Close liquid H2, mixed liquor H3, mixed liquor H4；
(30) SrCl for 0.21mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.94mol/L's
BiCl3Solution is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(31) Substance P is added in mixed liquor J1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material Q1, material Q1 is after the washing with alcohol that 100mL mass percent concentration is 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；
(32) SrCl for 0.41mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.74mol/L's
BiCl3Solution is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(33) material Q2 is added in mixed liquor J2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q3, material Q3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(34) SrCl for 0.61mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.54mol/L's
BiCl3Solution is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(35) material Q4 is added in mixed liquor J3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q5, material Q5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(36) SrCl for 0.81mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.34mol/L's
BiCl3Solution is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(37) material Q6 is added in mixed liquor J4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material Q7, material Q7 is after the washing with alcohol that 100mL mass percent concentration is 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；
(38) by 26.75 grams of ZnCl2With 9.27 grams of SbCl3It 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；
(39) by 12.07 grams of NaOH and 7.46 gram of Na2CO3It is added in 800mL deionized water, under the conditions of 1000r/min
Stirring 10 minutes, is divided into 5 parts of equivalent, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4 after shaking up；
(40) under 1000r/min stirring condition, mixed liquor L1 is added drop-wise in mixed liquor K1, obtains mixed liquor X1, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X1～
10.0, obtain mixed liquor Y1；
(41) NiCl for 0.27mol/L by 40mL molar concentration2Solution is added in mixed liquor Y1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z1；
(42) material Q is added in mixed liquor Z1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material R1, material R1 is after the washing with alcohol that 100mL mass percent concentration is 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；
(43) under 1000r/min stirring condition, mixed liquor L2 is added drop-wise in mixed liquor K2, obtains mixed liquor X2, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X2～
10.0, obtain mixed liquor Y2；
(44) NiCl for 0.47mol/L by 50mL molar concentration2Solution is added in mixed liquor Y2, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z2；
(45) material R2 is added in mixed liquor Z2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R3, material R3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(46) under 1000r/min stirring condition, mixed liquor L3 is added drop-wise in mixed liquor K3, obtains mixed liquor X3, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X3～
10.0, obtain mixed liquor Y3；
(47) NiCl for 0.67mol/L by 60mL molar concentration2Solution is added in mixed liquor Y3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z3；
(48) material R4 is added in mixed liquor Z3, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R5, material R5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(49) under 1000r/min stirring condition, mixed liquor L4 is added drop-wise in mixed liquor K4, obtains mixed liquor X4, with rubbing
Your concentration is the hydrochloric acid solution of 0.01mol/L and the NaOH solution of 0.01mol/L is adjusted to 9.5 by the pH value of mixed liquor X4～
10.0, obtain mixed liquor Y4；
(50) NiCl for 0.87mol/L by 70mL molar concentration2Solution is added in mixed liquor Y4, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Z4；
(51) material R6 is added in mixed liquor Z4, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material R7, material R7 is after the washing with alcohol that 100mL mass percent concentration is 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 vanadium pentoxide catalyst removing dimethylformamide for supercritical water oxidation.
The support type five that for supercritical water oxidation remove dimethylformamide that with the inventive method be obtained is presented herein below
V 2 O catalyst has carried out oxidation fall in afterflow fixed bed supercritical reaction device to the waste water containing dimethylformamide
Solution test, further illustrates the present invention.
It is anti-that the support type vanadium pentoxide catalyst that the inventive method is obtained is seated in continuously current flow fixed bed supercritical water
Answer in device, Degrading experiment has been carried out to the waste water containing dimethylformamide, result shows to be filled with this support type five oxidation two
The continuously current flow fixed bed supercritical water reaction device of vanadium catalyst can efficiently remove the dimethylformamide in waste water, when in waste water
Dimethylformamide concentration when being 36.4mg/L, be 365 DEG C in temperature, pressure is 25.5MPa, the time of staying is 37 seconds anti-
Under the conditions of answering, the dimethylformamide concentration in water outlet after process is reduced to 4.9mg/L.
Claims (1)
1. a kind of support type vanadium pentoxide catalyst removing dimethylformamide for supercritical water oxidation, its feature exists
In preparing comprising the following steps that of this catalyst method：
(1) put in 500mL acetone after the 133g vanadium oxide particles 300mL deionized water wash being 4～6mm by particle diameter
Soak 1h, remove liquid after filtration and obtain material M0, material M0 obtains material M1 after 300mL deionized water wash, by material
M1 puts in the hydrochloric acid solution that 300mL molar concentration is 2.5mol/L and soaks 0.5h, removes liquid and obtain material M2 after filtration,
Dry at 85 DEG C after material M2 300mL deionized water wash, then the washing with alcohol being 95% with 500mL mass percent concentration
Place 1.5h in dry case, obtain material M3, material M3 is added to the AgNO that 250mL molar concentration is 2.67mol/L3Solution
In, temperature be 65 DEG C shaking table in shake 75 minutes, be filtered to remove liquid after being cooled to room temperature and obtain material M4, material M4 warp
100mL mass percent concentration be 97% washing with alcohol after in 76 DEG C of drying baker place 140 minutes, be subsequently placed in Muffle
In stove under the conditions of 488 DEG C roasting 72 minutes, obtain material M；
(2) 4.88 grams of Polyvinylpyrrolidone and methanol solution that 600mL mass percent concentration is 80% are added to volume
For in 1000mL conical flask, stir 10 minutes under the conditions of 1000r/min, after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor A 1,
Mixed liquor A 2, mixed liquor A 3；
(3) 0.6327 gram of palladium chloride and 180mL concentrated hydrochloric acid are entered to volume for, in 500mL conical flask, being 75 DEG C in temperature
In water-bath shake 20 minutes, then in 120 DEG C of drying baker place 140 minutes, after being cooled to room temperature add 200mL go from
Sub- water, stirs 3 minutes under the conditions of 1000r/min, is divided into 3 parts of equivalent after shaking up, and obtains mixed liquid B 1, mixed liquid B 2, mixing
Liquid B3；
(4) 1.69 gram of three rhodium trichloride hydrate and 750mL deionized water being added to volume is in 1000mL conical flask,
Stir 3 minutes under the conditions of 1000r/min, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor A B1, mixed liquor A B2, mixed liquor A B3；
(5) sodium borohydride solution being 0.64mol/L by mixed liquor A 1, mixed liquor A B1 and 15mL molar concentration is added to mixing
In liquid B1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C1；
(6) material M is added in mixed liquor C1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material N1, material N1 is dry at 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；
(7) sodium borohydride solution being 054mol/L by mixed liquor A 2, mixed liquor A B2 and 13mL molar concentration is added to mixed liquor
In B2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C2；
(8) material N2 is added in mixed liquor C2, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material N3, material N3 is dry at 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；
(9) sodium borohydride solution being 0.44mol/L by mixed liquor A 3, mixed liquor A B3 and 11mL molar concentration is added to mixing
In liquid B3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor C3；
(10) material N4 is added in mixed liquor C3, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material N5, material N5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(11) by 5.24 grams of CuCl2With 7.41 grams of CdCl2It is added in 850mL ethanol, under the conditions of 1000r/min, stir 3 points
Clock, adds 5mL concentrated nitric acid, is divided into 5 parts of equivalent after shaking up, and obtains mixed liquor D1, mixed liquor D2, mixed liquor D3, mixed liquor D4, mixes
Close liquid D5；
(12) 4.39 grams of carbamide and 0.46 gram of ammonium fluoride are added in mixed liquor D1, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E1；
(13) material N is added in mixed liquor E1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material O1, material O1 is dry at 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；
(14) 4.29 grams of carbamide and 0.44 gram of ammonium fluoride are added in mixed liquor D2, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E2；
(15) material O2 is added in mixed liquor E2, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material O3, material O3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(16) 4.19 grams of carbamide and 0.42 gram of ammonium fluoride are added in mixed liquor D3, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E3；
(17) material O4 is added in mixed liquor E3, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material O5, material O5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(18) 4.09 grams of carbamide and 0.40 gram of ammonium fluoride are added in mixed liquor D4, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E4；
(19) material O6 is added in mixed liquor E4, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material O7, material O7 is after the washing with alcohol that 100mL mass percent concentration is 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 O8；
(20) 3.99 grams of carbamide and 0.38 gram of ammonium fluoride are added in mixed liquor D5, under the conditions of 1000r/min, stir 3 points
Clock, obtains mixed liquor E5；
(21) material O8 is added in mixed liquor E5, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material O9, material O9 is after the washing with alcohol that 100mL mass percent concentration is 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；
(22) by positive for 5.07 grams of metatitanic acids four fourth fat being added in 750mL dehydrated alcohol under 1000r/min stirring condition,
Stir 5 minutes under the conditions of 1000r/min, be subsequently adding 4mL concentrated nitric acid, after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor F1, mix
Close liquid F2, mixed liquor F3；
(23) 3.7mL tetraethyl orthosilicate and 13mL acetylacetone,2,4-pentanedione are added in mixed liquor F1, stir under the conditions of 1000r/min
Mix 3 minutes, obtain mixed liquor G1；
(24) material O is added in mixed liquor G1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain Substance P 1, Substance P 1 is dry at 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；
(25) 3.5mL 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；
(26) Substance P 2 is added in mixed liquor G2, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains Substance P 3, Substance P 3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(27) 3.3mL tetraethyl orthosilicate and 11mL acetylacetone,2,4-pentanedione are added in mixed liquor F3, stir under the conditions of 1000r/min
Mix 3 minutes, obtain mixed liquor G3；
(28) Substance P 4 is added in mixed liquor G3, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains Substance P 5, Substance P 5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(29) by 6.35 grams of SnCl4Being added to volume with the sodium citrate solution that 800mL mass percent concentration is 10% is
In 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, be divided into 4 parts of equivalent after shaking up, obtain mixed liquor H1, mixing
Liquid H2, mixed liquor H3, mixed liquor H4；
(30) SrCl for 0.21mol/L by 30mL molar concentration2Solution and 70mL molar concentration are the BiCl of 0.94mol/L3Molten
Liquid is added in mixed liquor H1, stirs 3 minutes, obtain mixed liquor J1 under the conditions of 1000r/min；
(31) Substance P is added in mixed liquor J1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material Q1, material Q1 is dry at 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；
(32) SrCl for 0.41mol/L by 40mL molar concentration2Solution and 60mL molar concentration are the BiCl of 0.74mol/L3Molten
Liquid is added in mixed liquor H2, stirs 3 minutes, obtain mixed liquor J2 under the conditions of 1000r/min；
(33) material Q2 is added in mixed liquor J2, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material Q3, material Q3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(34) SrCl for 0.61mol/L by 50mL molar concentration2Solution and 50mL molar concentration are the BiCl of 0.54mol/L3Molten
Liquid is added in mixed liquor H3, stirs 3 minutes, obtain mixed liquor J3 under the conditions of 1000r/min；
(35) material Q4 is added in mixed liquor J3, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material Q5, material Q5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(36) SrCl for 0.81mol/L by 60mL molar concentration2Solution and 40mL molar concentration are the BiCl of 0.34mol/L3Molten
Liquid is added in mixed liquor H4, stirs 3 minutes, obtain mixed liquor J4 under the conditions of 1000r/min；
(37) material Q6 is added in mixed liquor J4, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material Q7, material Q7 is after the washing with alcohol that 100mL mass percent concentration is 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；
(38) by 26.75 grams of ZnCl2With 9.27 grams of SbCl3It 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；
(39) by 12.07 grams of NaOH and 7.46 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 5 parts of equivalent, obtain mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4；
(40) under 1000r/min stirring condition, mixed liquor L1 is added drop-wise in mixed liquor K1, obtains mixed liquor X1, dense with mole
Spend the hydrochloric acid solution for 0.01mol/L and the pH value of mixed liquor X1 is adjusted to 9.5～10.0 by the NaOH solution of 0.01mol/L, obtain
To mixed liquor Y1；
(41) NiCl for 0.27mol/L by 40mL molar concentration2Solution is added in mixed liquor Y1, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z1；
(42) material Q is added in mixed liquor Z1, temperature be 48 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material R1, material R1 is dry at 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；
(43) under 1000r/min stirring condition, mixed liquor L2 is added drop-wise in mixed liquor K2, obtains mixed liquor X2, dense with mole
Spend the hydrochloric acid solution for 0.01mol/L and the pH value of mixed liquor X2 is adjusted to 9.5～10.0 by the NaOH solution of 0.01mol/L, obtain
To mixed liquor Y2；
(44) NiCl for 0.47mol/L by 50mL molar concentration2Solution is added in mixed liquor Y2, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z2；
(45) material R2 is added in mixed liquor Z2, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material R3, material R3 is after the washing with alcohol that 100mL mass percent concentration is 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；
(46) under 1000r/min stirring condition, mixed liquor L3 is added drop-wise in mixed liquor K3, obtains mixed liquor X3, dense with mole
Spend the hydrochloric acid solution for 0.01mol/L and the pH value of mixed liquor X3 is adjusted to 9.5～10.0 by the NaOH solution of 0.01mol/L, obtain
To mixed liquor Y3；
(47) NiCl for 0.67mol/L by 60mL molar concentration2Solution is added in mixed liquor Y3, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z3；
(48) material R4 is added in mixed liquor Z3, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material R5, material R5 is after the washing with alcohol that 100mL mass percent concentration is 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；
(49) under 1000r/min stirring condition, mixed liquor L4 is added drop-wise in mixed liquor K4, obtains mixed liquor X4, dense with mole
Spend the hydrochloric acid solution for 0.01mol/L and the pH value of mixed liquor X4 is adjusted to 9.5～10.0 by the NaOH solution of 0.01mol/L, obtain
To mixed liquor Y4；
(50) NiCl for 0.87mol/L by 70mL molar concentration2Solution is added in mixed liquor Y4, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Z4；
(51) material R6 is added in mixed liquor Z4, temperature be 48 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material R7, material R7 is after the washing with alcohol that 100mL mass percent concentration is 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 vanadium pentoxide catalyst of dimethylformamide in supercritical water oxidation.
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