CN114054098A - Method for preparing residual chlorine-free UiO-66 supported noble metal catalyst to avoid generation of dioxin - Google Patents
Method for preparing residual chlorine-free UiO-66 supported noble metal catalyst to avoid generation of dioxin Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 244
- 239000003054 catalyst Substances 0.000 title claims abstract description 235
- 239000013207 UiO-66 Substances 0.000 title claims abstract description 219
- 238000000034 method Methods 0.000 title claims abstract description 195
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 title claims abstract 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000000460 chlorine Substances 0.000 claims abstract description 151
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 151
- 238000005406 washing Methods 0.000 claims abstract description 53
- 239000003513 alkali Substances 0.000 claims abstract description 38
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims description 18
- 239000010935 stainless steel Substances 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 40
- 230000000382 dechlorinating effect Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000006298 dechlorination reaction Methods 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 231100000167 toxic agent Toxicity 0.000 abstract description 3
- 239000003440 toxic substance Substances 0.000 abstract description 3
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 201
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 85
- 230000003197 catalytic effect Effects 0.000 description 74
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 72
- 230000000694 effects Effects 0.000 description 41
- 239000007789 gas Substances 0.000 description 38
- 238000001514 detection method Methods 0.000 description 35
- 125000001309 chloro group Chemical group Cl* 0.000 description 30
- 239000012855 volatile organic compound Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 150000001555 benzenes Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000012696 Pd precursors Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- B01D2257/00—Components to be removed
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- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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Abstract
The invention discloses a method for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid the generation of dioxin, which is characterized by comprising the following steps: dechlorinating before preparing UiO-66 supported noble metal catalyst; or dechlorination in the process of preparing the UiO-66 supported noble metal catalyst; or dechlorination after the UiO-66 supported noble metal catalyst is prepared. Wherein, the chlorine removal before the preparation of the UiO-66 supported noble metal catalyst is realized by replacing a chlorine-containing zirconium source used for preparing the UiO-66 supported noble metal before the preparation, thereby achieving the purpose of removing chlorine; the chlorine removal in the process of preparing the UiO-66 supported noble metal catalyst is to add a precipitator to remove chlorine in the preparation process; the chlorine removal after the UiO-66 noble metal-loaded catalyst is prepared is to carry out alkali washing on the prepared UiO-66 noble metal-loaded catalyst, thereby achieving the purpose of chlorine removal. Compared with the traditional degradation of benzene series by UiO-66 loaded noble metal, the generation of chlorinated by-products (such as polychlorobenzene) in the degradation process of the benzene series can be reduced by removing chlorine, and the possibility of generating dioxin which is a highly toxic substance is reduced.
Description
Technical Field
The invention relates to the field of removing residual chlorine of a catalyst, in particular to a method for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid generation of dioxin.
Background
The emission of Volatile Organic Compounds (VOCs) is a main cause of composite air pollution in China. VOCs have been shown to be important precursors for ozone and PM2.5 formation. Thus, the removal of VOCs is imminent. The catalytic oxidation technology is one of the main technical means for removing VOCs, and the key point of the catalytic oxidation is to search for a high-efficiency and economical catalyst. Metal organic framework materials, especially the zirconium-based metal organic framework UiO-66, are widely used for loading noble metal catalysts for the removal of VOCs due to their higher thermal stability. However, a large amount of chlorine species remains in the traditionally synthesized UiO-66, and degradation of VOCs, especially benzene series, after noble metal loading, produces a large amount of chlorinated by-products (polychlorobenzene) and possibly a highly toxic species of dioxin.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for preparing a residual chlorine-free uo-66 supported noble metal catalyst to prevent the generation of dioxin.
The present invention provides a method for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid the generation of dioxin, having such characteristics that: dechlorinating before preparing UiO-66 supported noble metal catalyst; or dechlorination in the process of preparing the UiO-66 supported noble metal catalyst; or dechlorination after the UiO-66 supported noble metal catalyst is prepared. Wherein, the chlorine removal before the preparation of the UiO-66 supported noble metal catalyst is realized by replacing a chlorine-containing zirconium source used for preparing the UiO-66 supported noble metal before the preparation, thereby achieving the purpose of removing chlorine; the chlorine removal in the process of preparing the UiO-66 supported noble metal catalyst is to add a precipitator to remove chlorine in the preparation process; the chlorine removal after the UiO-66 noble metal-loaded catalyst is prepared is to carry out alkali washing on the prepared UiO-66 noble metal-loaded catalyst, thereby achieving the purpose of chlorine removal.
In the method for preparing the residual chlorine-free UiO-66 supported noble metal catalyst to avoid the generation of dioxin, the method can also have the following characteristics: the method for removing chlorine before preparing the UiO-66 supported noble metal catalyst specifically comprises the following substeps: step 1-1, completely dissolving a chlorine-free zirconium source and terephthalic acid in N, N-dimethylformamide to obtain a mixed solution; step 1-2, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the stainless steel reaction kettle into a forced air drying oven to react for 24 hours at 120 ℃ to obtain a reaction product; step 1-3, washing, filtering and drying a reaction product to obtain a solid UiO-66 carrier; and 1-4, loading a noble metal precursor on a solid UiO-66 carrier by using an ethylene glycol reduction method, reacting for 1-3 h at 120-180 ℃, performing centrifugal separation, washing and drying to obtain the supported noble metal UiO-66 catalyst without residual chlorine.
In the method for preparing the residual chlorine-free UiO-66 supported noble metal catalyst to avoid the generation of dioxin, the method can also have the following characteristics: wherein the chlorine-free zirconium source is any one of zirconium acid, zirconium acetate and zirconium sulfate.
In the method for preparing the residual chlorine-free UiO-66 supported noble metal catalyst to avoid the generation of dioxin, the method can also have the following characteristics: the method for removing chlorine in the process of preparing the UiO-66 supported noble metal catalyst specifically comprises the following substeps: step 2-1, weighing a zirconium source, and dissolving the zirconium source in N, N-dimethylformamide to obtain a clear solution; step 2-2, adding silver nitrate precipitate into the clear solution for 30min and filtering to obtain a mixed solution; step 2-3, adding terephthalic acid into the mixed solution, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining after complete dissolution, and placing the stainless steel reaction kettle into a forced air drying oven to react for 24 hours at 120 ℃ to obtain a reaction product; step 2-4, washing, filtering and drying the reaction product to obtain a solid UiO-66 carrier; and 2-5, loading a noble metal precursor on a solid UiO-66 carrier by using an ethylene glycol reduction method, reacting for 1-3 h at 120-180 ℃, performing centrifugal separation, washing and drying to obtain the supported noble metal UiO-66 catalyst without residual chlorine.
In the method for preparing the residual chlorine-free UiO-66 supported noble metal catalyst to avoid the generation of dioxin, the method can also have the following characteristics: wherein the zirconium source is zirconium chloride, and the molar ratio of silver nitrate to zirconium chloride is 4: 1-5: 1.
In the method for preparing the residual chlorine-free UiO-66 supported noble metal catalyst to avoid the generation of dioxin, the method can also have the following characteristics: the method for removing chlorine after preparing the UiO-66 supported noble metal catalyst specifically comprises the following substeps: step 3-1, completely dissolving a zirconium source and terephthalic acid in N, N-dimethylformamide to obtain a mixed solution; 3-2, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the stainless steel reaction kettle into a forced air drying oven to react for 24 hours at 120 ℃ to obtain a reaction product; step 3-3, washing, filtering and drying the reaction product to obtain a solid UiO-66 carrier; step 3-4, putting the solid UiO-66 carrier into hot alkali liquor for washing, centrifugally separating and drying; and 3-5, loading a noble metal precursor on a solid UiO-66 carrier by using an ethylene glycol reduction method, reacting for 1-3 h at 120-180 ℃, performing centrifugal separation, washing and drying to obtain the supported noble metal UiO-66 catalyst without residual chlorine.
In the method for preparing the residual chlorine-free UiO-66 supported noble metal catalyst to avoid the generation of dioxin, the method can also have the following characteristics: wherein the zirconium source is zirconium chloride.
In the method for preparing the residual chlorine-free UiO-66 supported noble metal catalyst to avoid the generation of dioxin, the method can also have the following characteristics: wherein the alkali liquor is any one of dilute ammonia water, sodium hydroxide solution and potassium hydroxide solution, and the pH value of the alkali liquor is between 8.0 and 10.0.
Action and Effect of the invention
The method for preparing the UO-66 supported noble metal catalyst free of residual chlorine to avoid the generation of dioxin comprises dechlorinating before preparing the UO-66 supported noble metal catalyst, or dechlorinating in the process of preparing the UO-66 supported noble metal catalyst, or dechlorinating after preparing the UO-66 supported noble metal catalyst. Wherein, the chlorine removal before the preparation of the UiO-66 supported noble metal catalyst is realized by replacing a chlorine-containing zirconium source used for preparing the UiO-66 supported noble metal before the preparation, thereby achieving the purpose of removing chlorine; the chlorine removal in the process of preparing the UiO-66 supported noble metal catalyst is to add a precipitator to remove chlorine in the preparation process; the chlorine removal after the UiO-66 noble metal-loaded catalyst is prepared is to carry out alkali washing on the prepared UiO-66 noble metal-loaded catalyst, thereby achieving the purpose of chlorine removal.
Compared with the traditional method for degrading benzene series by using UO-66 supported noble metal catalyst without residual chlorine, the method for preparing the residual chlorine-free UO-66 supported noble metal catalyst to avoid the generation of dioxin can reduce the generation of chlorinated byproducts (such as polychlorinated benzene) in the degradation process of the benzene series by removing chlorine and reduce the possibility of generating dioxin which is a highly toxic substance.
Drawings
FIG. 1 is a graph of the catalytic activity of a UiO-66 supported noble metal catalyst for removing residual chlorine versus VOCs as a function of reaction temperature in example 1 of the present invention;
FIG. 2 is a graph showing the change of catalytic activity of the UiO-66 supported noble metal catalyst for removing residual chlorine in example 3 of the present invention with respect to toluene with respect to the reaction temperature;
FIG. 3 is a graph of the catalytic activity of the UiO-66 supported noble metal catalyst for removing residual chlorine in example 4 of the present invention on toluene as a function of reaction temperature.
FIG. 4 is an X-ray diffraction pattern of a UiO-66 supported noble metal catalyst with no residual chlorine removed according to the comparative example of the present invention;
FIG. 5 is a graph of the catalytic activity of the UiO-66 supported noble metal catalyst without removing residual chlorine versus VOCs of the comparative example of the present invention as a function of reaction temperature; and
FIG. 6 is a statistical plot of chlorobenzene production after VOCs catalysis by UiO-66 supported noble metal catalyst without residual chlorine removal in comparative examples of the invention.
Detailed Description
In order to make the technical means, creation features, achievement objects and effects of the present invention easy to understand, the following embodiments are provided to describe the method for preparing the residual chlorine-free UiO-66 supported noble metal catalyst to avoid the generation of dioxin in combination with the accompanying drawings.
The chemicals and instruments used in the following examples are commercially available.
< example 1>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The method for preparing the non-chlorine residual UiO-66 supported noble metal catalyst to avoid the generation of dioxin in the embodiment is specifically as follows: (a) chlorine is removed before the UiO-66 supported noble metal catalyst is prepared. The method specifically comprises the following steps:
step S1-1, completely dissolving zirconium nitrate and terephthalic acid in N, N-dimethylformamide to obtain a mixed solution;
step S1-2, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the stainless steel reaction kettle into a forced air drying oven to react for 24 hours at 120 ℃ to obtain a reaction product;
step S1-3, washing, filtering and drying the reaction product to obtain a solid zirconium-based UiO-66 carrier;
and step S1-4, loading Pd and Pt precursors onto a solid UiO-66 carrier by using an ethylene glycol reduction method, reacting for 2 hours at 150 ℃, performing centrifugal separation, washing and drying to obtain the supported noble metal UiO-66 catalyst without residual chlorine.
In this embodiment, the specific process of evaluating the activity of the supported noble metal UiO-66 catalyst in catalyzing VOCs is as follows:
the activity evaluation of the catalyst was carried out in a fixed bed continuous flow differential reactor, the reaction tube being a U-shaped quartz glass reaction tube having an inner diameter of 4mm and an outer diameter of 6mm and a catalyst loading of 100 mg.
The composition of VOCs raw material gas is as follows: 1000ppm VOCs, 20% O2The equilibrium gas is Ar, the gas flow rate is 50ml/min, VOCs and byproducts in the product gas after 30min of reaction are analyzed on line by a GC-2060 gas chromatograph provided with a hydrogen flame ion detector, and the reaction activity is expressed by the conversion rate of the VOCs.
Wherein, benzene, toluene and xylene are respectively used as the VOCs, and the corresponding detection results are shown in table 1.
FIG. 1 is a graph of the catalytic activity of the UiO-66 supported noble metal catalyst for removing residual chlorine versus VOCs of this example as a function of reaction temperature.
As shown in fig. 1, the results show that the noble metal catalyst supported by UiO-66 without residual chlorine prepared in this example has better catalytic activity, and the detection of the exhaust gas does not detect the production of chlorinated byproducts such as chlorobenzene.
< example 2>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The method for preparing the non-chlorine residual UiO-66 supported noble metal catalyst to avoid the generation of dioxin in the embodiment is specifically as follows: (a) chlorine is removed before the UiO-66 supported noble metal catalyst is prepared. The procedure was analogous to example 1, except that the zirconium source was zirconium sulfate.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst without residual chlorine in catalyzing VOCs was the same as in example 1. The result shows that the noble metal catalyst loaded by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 3>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The method for preparing the non-chlorine residual UiO-66 supported noble metal catalyst to avoid the generation of dioxin in the embodiment is specifically as follows: (b) chlorine is removed in the process of preparing the UiO-66 supported noble metal catalyst. The specific process comprises the following steps:
and step S2-1, obtaining a clear solution after the zirconium chloride is completely dissolved in the N, N-dimethylformamide solvent.
And step S2-2, adding silver nitrate with the molar ratio of 4:1 to zirconium chloride into the clarified solution for precipitation for 30min and filtering to obtain a mixed solution.
And step S2-3, adding terephthalic acid into the mixed solution, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining after the terephthalic acid is completely dissolved, and placing the stainless steel reaction kettle into an air-blowing drying oven to react for 24 hours at 120 ℃ to obtain a reaction product.
And step S2-4, washing, filtering and drying the reaction product to obtain a solid UiO-66 carrier.
And step S2-5, loading Pt and Pd precursors on a solid UiO-66 carrier by an ethylene glycol reduction method, reacting for 2 hours at 120 ℃, performing centrifugal separation, washing and drying to obtain the supported noble metal UiO-66 catalyst without residual chlorine.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1.
FIG. 2 is a graph showing the change in catalytic activity of the UiO-66 supported noble metal catalyst for removing residual chlorine in this example with respect to toluene with respect to the reaction temperature.
As shown in fig. 2, the results show that the noble metal catalyst supported by UiO-66 without residual chlorine prepared in this example has better catalytic activity for toluene, and no production of chloro-byproducts such as chlorobenzene is detected for tail gas detection.
< example 4>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The method for preparing the uo-66 supported noble metal catalyst containing no residual chlorine to avoid the generation of dioxin in this example was carried out in a similar manner to example 3 except that the molar ratio of silver nitrate to zirconium chloride was 4.5:1 and the reaction conditions in step S2-5 were 180 ℃ for 1 hour.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1.
FIG. 3 is a graph showing the change in catalytic activity of the UiO-66 supported noble metal catalyst for removing residual chlorine in toluene with the reaction temperature in this example.
As shown in fig. 3, the results show that the noble metal catalyst supported by UiO-66 without residual chlorine prepared in this example has better catalytic activity for toluene, and no production of chloro-byproducts such as chlorobenzene is detected for tail gas detection.
< example 5>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The method for preparing the uo-66-supported noble metal catalyst free of residual chlorine to avoid the generation of dioxin in this example was carried out in a similar manner to example 3, except that the molar ratio of silver nitrate to zirconium chloride was 5:1, and the reaction conditions in step S2-5 were 180 ℃ for 1 hour.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 6>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The method for preparing the non-chlorine residual UiO-66 supported noble metal catalyst to avoid the generation of dioxin in the embodiment is specifically as follows: (c) chlorine is removed after the UiO-66 supported noble metal catalyst is prepared. The specific process comprises the following steps:
step S3-1, completely dissolving a zirconium source and terephthalic acid in N, N-dimethylformamide to obtain a mixed solution;
step S3-2, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the stainless steel reaction kettle into a forced air drying oven to react for 24 hours at 120 ℃ to obtain a reaction product;
step S3-3, washing, filtering and drying the reaction product to obtain a solid UiO-66 carrier;
step S3-4, washing the solid UiO-66 carrier in dilute ammonia water at 35 ℃ and pH 8 for 12h, centrifuging and drying;
and step S3-5, loading Pt and Pd precursors onto a solid UiO-66 carrier by using an ethylene glycol reduction method, reacting for 2 hours at 150 ℃, performing centrifugal separation, washing and drying to obtain the supported noble metal UiO-66 catalyst without residual chlorine.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 7>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6 except that the alkali solution was a potassium hydroxide solution having a pH of 9. The reaction conditions in step S3-5 were 120 ℃ for 2 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 8>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6, except that the alkali solution was a sodium hydroxide solution having a pH of 10. The reaction conditions in step S3-5 were 180 ℃ for 2 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 9>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6, except that the alkali solution was diluted ammonia water having a pH of 8 and a temperature of 40 ℃, and the washing time was 12 hours. The reaction conditions in step S3-5 were 120 ℃ for 1 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 10>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6, except that the alkali solution was a sodium hydroxide solution having a pH of 9 and a temperature of 40 ℃, and the washing time was 12 hours. The reaction conditions in step S3-5 were 150 ℃ for 1 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 11>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to example 6, except that the alkali solution was a potassium hydroxide solution having a pH of 10 and a temperature of 40 ℃, and the washing time was 12 hours. The reaction conditions in step S3-5 were 180 ℃ for 1 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 12>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6, except that the alkali solution was diluted ammonia water having a pH of 8 and a temperature of 45 c, and the washing time was 12 hours. The reaction conditions in step S3-5 were 120 ℃ for 3 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 13>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6, except that the alkali solution was a sodium hydroxide solution having a pH of 9 and a temperature of 45 c, and the washing time was 12 hours. The reaction conditions in step S3-5 were 150 ℃ for 3 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 13>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6, except that the alkali solution was a sodium hydroxide solution having a pH of 9 and a temperature of 45 c, and the washing time was 12 hours. The reaction conditions in step S3-5 were 150 ℃ for 3 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 14>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to example 6, except that the alkali solution was potassium hydroxide solution having a pH of 10 and a temperature of 45 c, and the washing time was 12 hours. The reaction conditions in step S3-5 were 180 ℃ for 3 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 15>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6, except that the alkali solution was diluted ammonia water having a pH of 8 and a temperature of 35 c, and the washing time was 24 hours. The reaction conditions in step S3-5 were 120 ℃ for 1 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 16>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6, except that the alkali solution was diluted ammonia water having a pH of 9 and a temperature of 35 c, and the washing time was 24 hours. The reaction conditions in step S3-5 were 150 ℃ for 1 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 17>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to example 6, except that the alkali solution was a potassium hydroxide solution having a pH of 10 and a temperature of 35 c, and the washing time was 24 hours. The reaction conditions in step S3-5 were 180 ℃ for 1 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 18>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6, except that the alkali solution was a sodium hydroxide solution having a pH of 8 and a temperature of 40 ℃, and the washing time was 24 hours. The reaction conditions in step S3-5 were 120 ℃ for 1 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 19>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6, except that the alkali solution was a potassium hydroxide solution having a pH of 9 and a temperature of 40 ℃, and the washing time was 24 hours. The reaction conditions in step S3-5 were 150 ℃ for 2 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 20>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to example 6, except that the alkali solution was diluted ammonia water having a pH of 10 and a temperature of 40 ℃, and the washing time was 24 hours. The reaction conditions in step S3-5 were 180 ℃ for 2 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 21>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6, except that the alkali solution was diluted ammonia water having a pH of 8 and a temperature of 45 c, and the washing time was 24 hours. The reaction conditions in step S3-5 were 120 ℃ for 3 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 22>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6, except that the alkali solution was a sodium hydroxide solution having a pH of 9 and a temperature of 45 c, and the washing time was 24 hours. The reaction conditions in step S3-5 were 150 ℃ for 3 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 23>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6, except that the alkali solution was potassium hydroxide solution having a pH of 10 and a temperature of 45 c, and the washing time was 24 hours. The reaction conditions in step S3-5 were 180 ℃ for 3 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 24>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6 except that the alkali solution was diluted ammonia water having a pH of 8 and a temperature of 35 c and the washing time was 48 hours. The reaction conditions in step S3-5 were 150 ℃ for 2 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 25>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6, except that the alkali solution was a sodium hydroxide solution having a pH of 9 and a temperature of 35 c, and the washing time was 48 hours. The reaction conditions in step S3-5 were 150 ℃ for 2 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 26>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to avoid the generation of dioxin in this example was similar to example 6, except that the alkali solution was a potassium hydroxide solution having a pH of 10 and a temperature of 35 c, and the washing time was 48 hours. The reaction conditions in step S3-5 were 150 ℃ for 2 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 27>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6 except that the alkali solution was diluted ammonia water having a pH of 8 and a temperature of 40 c and the washing time was 48 hours. The reaction conditions in step S3-5 were 120 ℃ for 2 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 28>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6 except that the alkali solution was diluted ammonia water having a pH of 9 and a temperature of 40 c and the washing time was 48 hours. The reaction conditions in step S3-5 were 150 ℃ for 2 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 29>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6, except that the alkali solution was diluted ammonia water having a pH of 10 and a temperature of 40 ℃, and the washing time was 48 hours. The reaction conditions in step S3-5 were 180 ℃ for 2 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 30>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6 except that the alkali solution was diluted ammonia water having a pH of 8 and a temperature of 45 c and the washing time was 48 hours. The reaction conditions in step S3-5 were 150 ℃ for 3 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 31>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to that of example 6 except that the alkali solution was diluted ammonia water having a pH of 9 and a temperature of 45 c and the washing time was 48 hours. The reaction conditions in step S3-5 were 150 ℃ for 3 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< example 32>
In this example, a method of preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation is provided.
The specific procedure of the method for preparing the residual chlorine-free UiO-66-supported noble metal catalyst to prevent the generation of dioxin in this example was similar to example 6, except that the alkali solution was diluted ammonia water having a pH of 10 and a temperature of 45 c, and the washing time was 48 hours. The reaction conditions in step S3-5 were 150 ℃ for 3 h.
In this example, the specific procedure for evaluating the activity of a supported noble metal UiO-66 catalyst containing no residual chlorine in catalytic toluene was the same as in example 1. The result shows that the noble metal catalyst supported by the UiO-66 without residual chlorine prepared in the embodiment has better catalytic activity on toluene, and the detection of tail gas does not detect the output of chloro byproducts such as chlorobenzene and the like.
< comparative example >
In this comparative example, a method of preparing a UiO-66 supported noble metal catalyst is provided.
The specific procedure for making a residual chlorine-free UiO-66 supported noble metal catalyst in this example is similar to that of example 1, except that the zirconium source is zirconium chloride.
In this comparative example, the specific procedure for evaluating the activity of the supported noble metal UiO-66 catalyst in catalyzing VOCs was the same as in example 1.
FIG. 4 is an X-ray diffraction pattern of the UiO-66 supported noble metal catalyst from which residual chlorine was not removed in this comparative example.
FIG. 5 is a graph of the catalytic activity of the UiO-66 supported noble metal catalyst without removing residual chlorine versus VOCs versus reaction temperature for this comparative example.
FIG. 6 is a statistical chart of the generation of chlorobenzene after VOCs catalysis by UiO-66 supported noble metal catalyst without residual chlorine removal in this comparative example.
As shown in fig. 4, 5 and 6, activity tests show that catalysts without removal of chlorine species in UiO-66 produce chlorine-containing byproducts, chlorobenzene, etc., during the treatment of VOCs.
Table 1 shows the detection of chlorinated byproducts of VOCs catalyzed by UiO-66 noble metal-supported catalyst prepared in the comparative example and each example.
TABLE 1
Effects and effects of the embodiments
The method for preparing a uo-66 supported noble metal catalyst free of residual chlorine to prevent dioxin generation according to examples 1 to 32 includes dechlorinating before preparing the uo-66 supported noble metal catalyst, or dechlorinating during preparing the uo-66 supported noble metal catalyst, or dechlorinating after preparing the uo-66 supported noble metal catalyst. Wherein, the chlorine removal before the preparation of the UiO-66 supported noble metal catalyst is realized by replacing a chlorine-containing zirconium source used for preparing the UiO-66 supported noble metal before the preparation, thereby achieving the purpose of removing chlorine; the chlorine removal in the process of preparing the UiO-66 supported noble metal catalyst is to add a precipitator to remove chlorine in the preparation process; the chlorine removal after the UiO-66 noble metal-loaded catalyst is prepared is to carry out alkali washing on the prepared UiO-66 noble metal-loaded catalyst, thereby achieving the purpose of chlorine removal.
Examples 1 to 32 relate to a method for preparing a uo-66 supported noble metal catalyst without residual chlorine to prevent dioxin from being generated, which can reduce the generation of chlorinated byproducts (such as polychlorobenzene) during the degradation of benzene and reduce the possibility of generation of dioxin, which is a highly toxic substance, through removal of chlorine, compared with the conventional method for degrading benzene by using a uo-66 supported noble metal.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (9)
1. A method for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation, comprising:
removing chlorine before preparing the UiO-66 supported noble metal catalyst; or
Removing chlorine in the process of preparing the UiO-66 supported noble metal catalyst; or
After the UiO-66 supported noble metal catalyst is prepared, chlorine is removed,
wherein, the chlorine removal before the preparation of the UiO-66 supported noble metal catalyst is to replace a chlorine-containing zirconium source used for preparing the UiO-66 supported noble metal before the preparation, thereby achieving the purpose of removing chlorine,
the chlorine removal in the process of preparing the UiO-66 supported noble metal catalyst is to add a precipitator in the preparation process to remove chlorine,
the chlorine removal after the UiO-66 noble metal-loaded catalyst is carried out by carrying out alkali washing on the prepared UiO-66 noble metal, so that the aim of removing chlorine is fulfilled.
2. The method of claim 1 for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation, wherein:
the method for removing chlorine before preparing the UiO-66 supported noble metal catalyst specifically comprises the following substeps:
step 1-1, completely dissolving a chlorine-free zirconium source and terephthalic acid in N, N-dimethylformamide to obtain a mixed solution;
step 1-2, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and putting the stainless steel reaction kettle into a forced air drying oven to react for 24 hours at 120 ℃ to obtain a reaction product;
step 1-3, washing, filtering and drying the reaction product to obtain a solid UiO-66 carrier;
and 1-4, loading a noble metal precursor on the solid UiO-66 carrier by using an ethylene glycol reduction method, reacting for 1-3 h at 120-180 ℃, performing centrifugal separation, washing and drying to obtain the supported noble metal UiO-66 catalyst without residual chlorine.
3. The method of claim 2 for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation, wherein:
wherein the chlorine-free zirconium source is any one of zirconium acid, zirconium acetate and zirconium sulfate.
4. The method of claim 1 for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation, wherein:
the method for removing chlorine in the process of preparing the UiO-66 supported noble metal catalyst specifically comprises the following substeps:
step 2-1, weighing a zirconium source, and dissolving the zirconium source in N, N-dimethylformamide to obtain a clear solution;
step 2-2, adding silver nitrate precipitate into the clarified solution for 30min and filtering to obtain a mixed solution;
step 2-3, adding terephthalic acid into the mixed solution, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining after complete dissolution, and placing the stainless steel reaction kettle into a forced air drying oven to react for 24 hours at 120 ℃ to obtain a reaction product;
step 2-4, washing, filtering and drying the reaction product to obtain a solid UiO-66 carrier;
and 2-5, loading a noble metal precursor on the solid UiO-66 carrier by using an ethylene glycol reduction method, reacting for 1-3 h at 120-180 ℃, performing centrifugal separation, washing and drying to obtain the supported noble metal UiO-66 catalyst without residual chlorine.
5. The method of claim 4 for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation, wherein:
wherein the zirconium source is zirconium chloride,
the molar ratio of the silver nitrate to the zirconium chloride is 4: 1-5: 1.
6. The method of claim 1 for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation, wherein:
the method for removing chlorine after the UiO-66 supported noble metal catalyst is prepared specifically comprises the following substeps:
step 3-1, completely dissolving a zirconium source and terephthalic acid in N, N-dimethylformamide to obtain a mixed solution;
3-2, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the stainless steel reaction kettle into a forced air drying oven to react for 24 hours at 120 ℃ to obtain a reaction product;
step 3-3, washing, filtering and drying the reaction product to obtain a solid UiO-66 carrier;
step 3-4, putting the solid UiO-66 carrier into hot alkali liquor for washing, centrifugally separating and drying;
and 3-5, loading a noble metal precursor on the solid UiO-66 carrier by using an ethylene glycol reduction method, reacting for 1-3 h at 120-180 ℃, performing centrifugal separation, washing and drying to obtain the supported noble metal UiO-66 catalyst without residual chlorine.
7. The method of claim 6 for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation, wherein:
wherein the zirconium source is desirably zirconium chloride.
8. The method of claim 6 for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation, wherein:
wherein the alkali liquor is any one of dilute ammonia water, sodium hydroxide solution and potassium hydroxide solution,
the pH value of the alkali liquor is 8.0-10.0.
9. The method of claim 6 for preparing a residual chlorine-free UiO-66 supported noble metal catalyst to avoid dioxin generation, wherein:
wherein the washing temperature is 35-45 ℃, and the washing time is 12-48 h.
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| CN1280030A (en) * | 1999-07-09 | 2001-01-17 | 户田工业株式会社 | Treating method for waste gas containing dipyryl |
| CN108786921A (en) * | 2018-04-26 | 2018-11-13 | 上海理工大学 | A kind of monatomic Pd@UiO-66 catalyst and its preparation method and application |
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|---|---|---|---|---|
| CN1280030A (en) * | 1999-07-09 | 2001-01-17 | 户田工业株式会社 | Treating method for waste gas containing dipyryl |
| CN108786921A (en) * | 2018-04-26 | 2018-11-13 | 上海理工大学 | A kind of monatomic Pd@UiO-66 catalyst and its preparation method and application |
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