CN111569877A - Catalyst and preparation method thereof - Google Patents
Catalyst and preparation method thereof Download PDFInfo
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- CN111569877A CN111569877A CN202010418646.7A CN202010418646A CN111569877A CN 111569877 A CN111569877 A CN 111569877A CN 202010418646 A CN202010418646 A CN 202010418646A CN 111569877 A CN111569877 A CN 111569877A
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- catalyst
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- mixed solution
- metal salt
- trivalent metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 45
- 150000003839 salts Chemical class 0.000 claims abstract description 40
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 239000010949 copper Substances 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 27
- 239000012266 salt solution Substances 0.000 abstract description 20
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 230000003647 oxidation Effects 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 14
- 239000002905 metal composite material Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- -1 copper-iron-aluminum Chemical compound 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 150000001879 copper Chemical class 0.000 description 5
- 150000002505 iron Chemical class 0.000 description 5
- 229910001428 transition metal ion Inorganic materials 0.000 description 5
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006385 ozonation reaction Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing a mixed solution from at least one of organic amine and ammonium salt, divalent metal salt and trivalent metal salt; (2) mixing a carrier with the mixed solution and carrying out crystallization reaction to prepare a precursor; (3) and roasting the precursor to prepare the catalyst. The preparation method of the catalyst according to the conception of the invention not only can slowly react the salt solution of the active component with the alkalescent solution, obviously reduce the size of the crystal nucleus of the layered multi-metal composite hydroxide generated by the reaction, and obviously improve the activity of the prepared ozone oxidation catalyst, thereby greatly improving the removal rate of COD, realizing the firm combination of metal ions and carriers, and simultaneously improving the dispersion degree of the active component.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a preparation method of a catalyst and the catalyst prepared by the method.
Background
The catalytic ozonation technology belongs to an important branch in advanced oxidation water treatment technology, and combines the strong oxidizing property of ozone and the adsorption and catalysis properties of a catalyst, so that the problem of incomplete degradation of organic matters can be effectively solved.
For the ozone catalytic oxidation technology, the key point is the preparation of the catalyst. Since the high preparation cost of the catalyst for catalytic oxidation of ozone in the prior art restricts the use thereof, it is required to provide a method for preparing the catalyst for catalytic oxidation of ozone at a low cost.
Disclosure of Invention
The invention aims to provide a catalyst and a preparation method thereof, wherein the preparation method comprises the step of slowly hydrolyzing at least one of organic amine and ammonium salt to slowly react a salt solution of divalent metal ions and trivalent metal ions with a weak alkaline solution of at least one of organic amine and ammonium salt, so that the size of a crystal nucleus of a layered multi-metal composite hydroxide generated by the reaction is obviously reduced, the activity of the prepared ozone oxidation catalyst is obviously improved, and the removal rate of COD is greatly improved.
According to an aspect of the present invention, there is provided a method for preparing a catalyst, the method comprising the steps of: (1) preparing a mixed solution from at least one of organic amine and ammonium salt, divalent metal salt and trivalent metal salt; (2) mixing a carrier with the mixed solution and carrying out crystallization reaction to prepare a precursor; (3) and roasting the precursor to prepare the catalyst.
According to an exemplary embodiment, the step (2) may include: impregnating the mixed solution on the support to obtain a mixture, and then subjecting the mixture to the crystallization reaction; and after the crystallization reaction, carrying out cooling operation, and then washing and drying the obtained solid to prepare the precursor.
According to an exemplary embodiment, the crystallization reaction may have a reaction temperature of 50 ℃ to 150 ℃ and a reaction time of 2h to 10 h.
According to an exemplary embodiment, a molar ratio of the divalent metal ion in the divalent metal salt to the trivalent metal ion in the trivalent metal salt may be in a range of 2:1 to 4: 1.
According to an exemplary embodiment, the content of the trivalent metal salt in the mixed solution may be determined such that the mass of the trivalent metal in the trivalent metal salt is 1% to 10% of the mass of the support.
According to an exemplary embodiment, the volume of the mixed solution may be a product of the mass of the carrier and the water absorption rate of the carrier.
According to an exemplary embodiment, in the step (1), the pH of the mixed solution may be 8 to 10.
According to an exemplary embodiment, the divalent metal salt may include a soluble divalent copper salt, and the trivalent metal salt may include a soluble iron salt. The soluble divalent copper salt may include at least one of a nitrate of copper, a sulfate of copper, and a chloride of copper, and the soluble iron salt may include at least one of a nitrate of iron, a sulfate of iron, and a chloride of iron. For example, the soluble divalent copper salt may include at least one of copper nitrate, copper sulfate, and copper chloride, and the soluble iron salt may include at least one of iron nitrate, iron sulfate, and iron chloride.
According to an exemplary embodiment, the organic amine may include at least one of urea, hexamethylenetetramine, cetyltrimethylammonium bromide, and polyacrylamide, and the ammonium salt may include at least one of ammonium carbonate and ammonium bicarbonate.
According to another aspect of the present invention, there is provided a catalyst prepared by one of the above-mentioned preparation methods.
Through the above brief description of the present inventive concept, the preparation method according to the present inventive concept slowly reacts the salt solution of the active components (divalent metal ions and trivalent metal ions) with the weakly alkaline solution of at least one of the organic amine and the ammonium salt by using at least one of the weakly alkaline organic amine and the ammonium salt, significantly reduces the size of the crystal nucleus of the layered multi-metal composite hydroxide generated by the reaction, significantly improves the activity of the prepared ozone oxidation catalyst, and thus greatly improves the COD removal rate.
In addition, according to the preparation method of the inventive concept, the precursor is synthesized in situ by impregnating the support in the mixed solution so that the active component enters the pores of the support in the form of a solution, and then allowing the mixed solution to directly perform a crystallization reaction on the support, wherein nuclei of the layered multi-metal composite hydroxide in the precursor contain not only the divalent metal and the trivalent metal but also the metal element in the support. Namely, the divalent metal and the trivalent metal form covalent bonds with metal elements in the carrier, so that the metal ions are firmly combined with the carrier, the service life of the ozone oxidation catalyst is obviously prolonged, the loss of active components is favorably prevented, and the overproof of the metal ions in effluent is avoided. In addition, the dispersion degree of the active components is also favorably improved.
In addition, the catalyst according to the invention adopts the cheap copper and iron catalyst for concerted catalysis, thereby realizing the preparation of the catalyst with wide application value and preparing the catalyst into the layered copper-iron-aluminum multi-metal composite compound. This reduces the production cost of the catalyst, and the catalyst can exhibit excellent catalytic oxidation activity of ozone in the catalytic oxidation reaction of ozone.
Detailed Description
Hereinafter, the inventive concept will be described in detail with reference to specific embodiments, however, the following exemplary embodiments are only intended to fully convey the inventive concept to those skilled in the art, and do not limit the scope of the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
The ozone catalytic oxidation reaction is a structure-sensitive reaction, and the catalytic performance of the catalyst used in the ozone catalytic oxidation reaction is related to the properties of the raw materials, the crystal grain size of the active components, the dispersibility of the active components and other factors. The smaller the crystal grain size of the active component, the higher the specific surface area of the crystal grain, the more the number of surface active sites and the higher the catalytic activity, and in addition, the higher the dispersibility of the active component and the higher the catalytic activity. The grain size and dispersibility of the active component are related to the preparation method. In addition, in the prior art, transition metal oxides are generally used as active components of catalysts, but the ions of the transition metals are not firmly combined with carriers and have poor dispersion state, so that the loss of the metal ions is serious, and the technical problems of low catalytic efficiency, short catalyst life, overproof metal ions in effluent and the like exist. Therefore, it is desirable to provide a method for preparing a catalyst for catalytic oxidation of ozone which can overcome the above technical problems.
The invention can realize the beneficial technical effects of reducing the loss of transition metal ions, improving the dispersibility of the transition metal ions and the like on the basis of reducing the production cost of the catalyst by preparing the layered multi-transition metal composite compound (the copper-iron-aluminum multi-metal composite compound). In addition, the inventive concept also uses transition metals copper and iron, which have low costs, as active components, thereby enabling the preparation of ozone catalysts having a wide range of application values.
Hereinafter, a method for preparing a catalyst for ozone oxidation according to the present inventive concept will be described in detail with reference to exemplary embodiments.
As will be described below, the present invention contemplates the use of the active component metals Cu, Fe in solution into γ -Al2O3The surface of the inner hole of the carrier is synthesized in situ with CuFeAl-LDHs/Al containing Cu, Fe and Al on the laminate2O3And roasting the precursor to form the catalyst containing Cu and Fe for catalytic ozonation. Therefore, the preparation method of the catalyst for catalytic oxidation of ozone according to the exemplary embodiments of the inventive concept may include (CuFeAl-LDHs/Al)2O3) A precursor preparation step and a catalyst preparation step.
2 3Preparation step of (CuFeAl-LDHs/AlO) precursor
Layered composite metal Hydroxides (LDHs) are novel inorganic functional materials, two-dimensional laminates of the Layered composite metal Hydroxides are longitudinally and orderly arranged to form a three-dimensional crystal structure, atoms on the laminates are combined by covalent bonds, and interlayer anions are combined with the laminates by ionic bonds and other weak chemical bonds. Trivalent cations on the LDHs laminate lead the skeleton of the laminate to carry positive charges, and anions with opposite charges between layers are balanced with the trivalent cations, so that the whole crystal is electrically neutral. The material is characterized by the controllability of the layer elements, the dispersion uniformity and the exchangeability of anions between layers.
Therefore, the invention introduces divalent transition metal ions and trivalent transition metal ions with ozone catalytic oxidation activity into the LDHs laminate, and the transition metal ions as active components and cocatalyst components can be highly dispersed and relatively stable in the LDHs precursor under the joint influence of the lowest lattice energy and the positioning effect of atoms in crystals.
Specifically, the invention contemplates (CuFeAl-LDHs/Al)2O3) The precursor preparation step may include preparation of a salt solution and impregnation of the support.
The salt solution for impregnating the support contemplated by the present invention may include at least one of an organic amine and/or an ammonium salt, a divalent metal salt, and a trivalent metal salt. The divalent and trivalent metal salts according to the present inventive concept slowly chemically react with at least one of the organic amines and/or ammonium salts to generate a hydroxide with a small grain size, which is decomposed into a corresponding oxide during a subsequent baking process, and the oxide is used as an active component. In the field of catalytic ozonation, active components are used to degrade organic matter, and thus active components may include those known in the art for treating wastewater and are not limited to the case of soluble salts of divalent copper and soluble salts of trivalent iron described in the specific examples of the present invention. That is, the specific form of the divalent metal ion and the trivalent metal ion included in the exemplary embodiments of the present invention may be at least one of a transition metal compound, a rare earth metal compound, an alkali metal compound, and an alkaline earth metal compound, such as Mg2+、Ca2+、Sr2+、Ba2+、Zn2+、Mn2+And the like, and divalent metal ions such as Al3+、Cr3+、V3+、Ti3+And the like may be used. In addition, the divalent metal ions selected for use in the inventive concept include Cu in consideration of cost2+The trivalent metal ion comprises Fe3+But is not limited thereto. That is, the divalent metal salt according to the inventive concept may include a soluble divalent copper salt, the trivalent metal salt may include a soluble trivalent iron salt, and the case where the divalent metal salt includes a soluble divalent copper salt and the trivalent metal salt includes a soluble trivalent iron salt will be mainly described in the following description.
In addition, anions in the divalent metal salt and the trivalent metal salt according to exemplary embodiments of the inventive concept may include NO3 -、SO4 2-And Cl-But is not limited thereto. Thus, according to exemplary embodiments, the divalent metal salt of the inventive concept may include at least one of a nitrate of copper, a sulfate of copper, and a chloride of copper, and the trivalent metal salt may include at least one of a nitrate of iron, a sulfate of iron, and a chloride of iron. For example, the divalent metal salt may include at least one of copper nitrate, copper sulfate, and copper chloride, and the trivalent metal salt may include at least one of iron nitrate, iron sulfate, and iron chloride.
Further, as will be described below, in the salt solution including the soluble divalent metal salt, the soluble trivalent metal salt, and at least one of the organic amine and the ammonium salt, the addition amounts of the soluble divalent metal salt and the soluble trivalent metal salt may be determined in the following ratios: the mass of trivalent metal ions (e.g., iron ions) in the trivalent metal salt included in the formulated salt solution is a carrier (e.g., Al)2O3More preferably gamma-Al2O3) 1% -10% of the mass of (b), and the number of moles of divalent metal ions (e.g., copper ions) is 2 to 4 times, preferably 3 times the number of moles of trivalent metal ions (e.g., iron ions). For example, when the carrier has a mass of 100g, the mass of the trivalent metal ion (e.g., iron ion) included in the salt solution may be in the range of 1g to 10g, for example, in the range of 2g to 7g, in the range of 3g to 8g, or in the range of 5g to 9gWithin the range.
The organic amine and/or ammonium salt included in the salt solution according to an exemplary embodiment of the inventive concept may be used to generate hydrotalcite in a subsequent reaction. Here, the organic amine and/or the ammonium salt according to an exemplary embodiment may include a soluble organic amine and/or an ammonium salt, the organic amine may be at least one selected from the group consisting of urea, hexamethylenetetramine, cetyltrimethylammonium bromide, and polyacrylamide, and the ammonium salt may be at least one selected from the group consisting of ammonium carbonate and ammonium bicarbonate. However, exemplary embodiments of the inventive concept are not limited to the kinds of organic amines and ammonium salts. Further, the addition amount of the organic amine and/or ammonium salt according to the exemplary embodiment is not particularly limited as long as the pH of the salt solution to be formulated can be controlled to 8 to 10 (preferably 8 to 9).
Here, the present invention contemplates using a soluble organic amine or ammonium salt having weak basicity instead of the strong basicity of NaOH and Na2CO3. When strongly basic NaOH and Na are used2CO3In the presence of NaOH and Na2CO3The mixed solution of (A) and (B) reacts with a mixed salt solution of divalent metal ions and trivalent metal ions to form layered multi-metal composite hydroxide nuclei, the reaction being due to NaOH and Na2CO3The strong basicity of the mixed solution and the intense heat generation cause the generated crystal nucleus of the layered multi-metal composite hydroxide to be oversized, so that the activity of the prepared catalyst is low, and the mixed slurry containing the crystal nucleus of the layered multi-metal composite hydroxide with the oversized crystal nucleus reacts with the carrier again, which is not favorable for improving the dispersion degree of the active component. However, the weakly alkaline soluble organic amine or ammonium salt used according to the concept of the invention can be slowly decomposed in the hydrothermal process, so that the pH value of the reaction system can be automatically regulated, the alkalinity of the alkali liquor is reduced, the purpose of slow heat release of the reaction between the mixed salt solution of the divalent metal ions and the trivalent metal ions and the weakly alkaline solution can be realized, the grain size of the crystal nucleus of the layered multi-metal composite compound generated by the reaction is effectively controlled, and the activity of the catalyst is improved, namely the COD removal rate of the wastewater is improved.
After formulating the salt solution according to the inventive concept according to the above described aspects, impregnation of the support may be performed.
The carrier according to an exemplary embodiment of the inventive concept may include Al2O3And may specifically include γ -Al2O3. The carrier should have a small particle size and thus a large specific surface area in order to maximally adsorb the active components on its surface, increase the loading amount, and improve the catalytic activity. Thus, the carrier according to an exemplary embodiment may include gamma-Al having spherical particles with a diameter of 3mm to 5mm2O3. However, the inventive concept is not limited to γ -Al2O3In the shape and specific dimensions of (A), e.g. gamma-Al2O3Or strip, clover, etc. Hereinafter, will be mainly directed to γ -Al2O3The inventive concept is described as a specific example of a carrier.
In addition, when gamma-Al having a certain shape and size is selected2O3After the support, the amount of the soluble trivalent metal salt added and the amount of the support added may be determined according to the content of the trivalent metal ion included in the salt solution prepared above. Specifically, with the gamma-Al2O3The loading amount of the trivalent metal ion in the salt solution (i.e., the mass percentage of the trivalent metal ion relative to the carrier in the salt solution) is 1% to 10% based on 100% by mass of the carrier, and the volume (mL) of the salt solution may be γ -Al2O3Product of carrier mass (g) and carrier water absorption (%). According to an example, the prepared salt solution may be immersed in Al in equal volume2O3Carrier (gamma-Al)2O3A carrier). Here, the term "isovolumetric impregnation" is understood to mean that the volume of saline solution (mL) is equal to γ -Al2O3Product of carrier mass (g) and carrier water absorption (%).
The impregnation of the support can be carried out according to the operations described above. In order to achieve a sufficient impregnation of the support in the salt solution, the impregnation time can be between 0.5h and 3 h. Thereafter, the crystallization reaction may be performed at a temperature of 50 ℃ to 150 ℃, preferably 50 ℃ to 100 ℃, and the reaction time of the crystallization reaction may be 2h to 10h, for example, 5h to 10h, 4h to 8h, 3h to 9 h.
After the preset time period, cooling, washing with deionized water to neutrality, drying at 80-120 deg.c for 2-6 hr to obtain (CuFeAl-LDHs/Al)2O3) And (3) precursor.
Preparation step of catalyst
Obtained according to the method described above (CuFeAl-LDHs/Al)2O3) After the precursor, a preparation step of the catalyst may be performed.
The preparation step of the catalyst according to the inventive concept may include the step of subjecting (CuFeAl-LDHs/Al) to a temperature of 350 deg.C-550 deg.C (preferably 350 deg.C-450 deg.C, more preferably 400 deg.C)2O3) Roasting the precursor for 2h-6h (preferably 4h-6h, more preferably 5h) to obtain (CuFeAl-LDHs/Al)2O3) The precursor is converted into corresponding composite metal oxide, and the finished catalyst of Cu/Fe highly dispersed catalytic ozonation is obtained.
The ozone oxidation catalyst for treating wastewater may be prepared according to the preparation method of the exemplary embodiment of the above inventive concept. The preparation method can not only make the salt solution of the active component slowly react with the alkalescent solution and obviously reduce the size of the crystal nucleus of the layered multi-metal composite hydroxide generated by the reaction, so that the activity of the prepared ozone oxidation catalyst is obviously improved, thereby greatly improving the removal rate of COD, but also can make the mixed solution directly synthesize the precursor on the carrier in situ, thereby forming covalent bonds between the active component and metal elements in the carrier, realizing the firm combination of metal ions and the carrier to solve the problem of copper ion loss, simultaneously reducing the cost of the catalyst and improving the dispersion degree of the active component.
Hereinafter, specific embodiments and comparative examples of the inventive concept will be described in detail. The carriers in the following examples and comparative examples are all spherical gamma-Al2O3A carrier having a diameter of 3mm to 5mm and a specific surface area of 200m2The water absorption of the carrier was 50%.
Example 1
(1) 86.98g of Cu (NO)3)2·3H2O (0.36mol), 72.32g Fe (NO)3)3·9H2Dissolving O (0.18mol) and cetyl trimethyl ammonium bromide in deionized water to prepare a mixed solution, and adjusting the volume of the mixed solution to 50mL, wherein the dosage of the cetyl trimethyl ammonium bromide is that the pH of the mixed solution is 8, and the Cu content is Cu2+With Fe3+In a molar ratio of 2: 1;
(2) immersing the mixed solution obtained in the step (1) in 100g of gamma-Al in the same volume2O3Dipping the carrier (0.98mol) for 0.5h, and then carrying out crystallization reaction at the temperature of 50 ℃ for 10 h; after 10h, cooling and taking out solid particles, washing the solid particles to be neutral by deionized water, and then drying for 6h at 80 ℃ to obtain (CuFeAl-LDHs/Al)2O3) A precursor, wherein the loading capacity of iron ions is 10%;
(3) roasting the precursor in the step (2) at the temperature of 350 ℃ for 6 hours to obtain (CuFeAl-LDHs/Al)2O3) The precursor is converted into a corresponding composite metal oxide, thereby preparing the Cu/Fe highly dispersed catalyst 1.
Comparative example 1
(1) 86.98g of Cu (NO)3)2·3H2O (0.36mol) and 72.32g Fe (NO)3)3·9H2Dissolving O (0.18mol) in deionized water to prepare a mixed solution, and adjusting the volume of the mixed solution to be 50mL and Cu2+With Fe3+In a molar ratio of 2: 1;
(2) immersing the mixed solution obtained in the step (1) in 100g of gamma-Al in the same volume2O3(0.98mol) on a carrier, and the dipping time is 0.5 h; then taking out the solid particles and drying the solid particles at 80 ℃ for 6 hours to obtain a precursor;
(3) and (3) roasting the precursor obtained in the step (2) at the temperature of 350 ℃ for 6 hours to obtain the comparative catalyst 1.
Comparative example 2
(1) 86.98g of Cu (NO)3)2·3H2O(0.36mol) and 72.32g of Fe (NO)3)3·9H2Dissolving O (0.18mol) in deionized water to prepare a mixed solution A. 34.56g of NaOH (0.864mol) and 38.16g of Na were added2CO3(0.36mol) is dissolved in deionized water to prepare a mixed solution B. The solution volumes of the mixed solution A and the mixed solution B are not limited as long as Cu (NO)3)2、Fe(NO3)3NaOH and Na2CO3The mixed solution A and the mixed solution B are completely dissolved, but the total volume of the mixed solution A and the mixed solution B is 50 mL; in addition, Cu2+With Fe3+In a molar ratio of 2: 1;
(2) adding the mixed solution A and the mixed solution B obtained in the step (1) into a full back-mixing rotary liquid membrane reactor simultaneously for reacting for 1-3 min, and then reacting with 100g of gamma-Al2O3Transferring the carriers (0.98mol) into a reaction kettle together, and reacting for 10 hours at 50 ℃; then, cooling, taking out solid particles, washing with deionized water, and drying at 80 ℃ for 6 hours to obtain a precursor;
(3) and (3) roasting the precursor in the step (2) at the temperature of 350 ℃ for 6h to obtain the comparative catalyst 2.
The ozone oxidation catalyst prepared in example 1 above and comparative catalysts 1 and 2 prepared in comparative examples 1 and 2 were evaluated in the ozone catalytic oxidation test of wastewater, which was used in a fixed reactor for treating wastewater having a COD content of about 100 mg/L. The evaluation conditions were: the adding amount of the catalyst is 1000g, the adding amount of the ozone is 70mg/L, and the hourly space velocity of the waste water liquid is 1h-1The ozone is continuously aerated by adopting an aeration disc, the reaction time is 5h, wherein the ozone adding amount (mg/L) is (ozone concentration (mg/L) × ozone volume flow rate (m)3H))/amount of treated water (m)3H), the ozone concentration is 100mg/L, the copper ion elution amount is detected by an atomic absorption spectrophotometer or an ICP (inductively Coupled Plasma Emission spectrometer) inductively Coupled Plasma spectrometer, and the performance evaluation results are shown in Table 1.
TABLE 1
Although a few embodiments of the present invention have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents.
Claims (10)
1. A preparation method of a catalyst is characterized by comprising the following steps:
(1) preparing a mixed solution from at least one of organic amine and ammonium salt, divalent metal salt and trivalent metal salt;
(2) mixing a carrier with the mixed solution and carrying out crystallization reaction to prepare a precursor;
(3) and roasting the precursor to prepare the catalyst.
2. The method of claim 1, wherein the step (2) comprises:
impregnating the mixed solution on the support to obtain a mixture, and then subjecting the mixture to the crystallization reaction;
and after the crystallization reaction, carrying out cooling operation, and then washing and drying the obtained solid to prepare the precursor.
3. The preparation method according to claim 2, wherein the crystallization reaction is carried out at a reaction temperature of 50 ℃ to 150 ℃ for 2h to 10 h.
4. The method according to claim 1, wherein a molar ratio of the divalent metal ion in the divalent metal salt to the trivalent metal ion in the trivalent metal salt is in a range of 2:1 to 4: 1.
5. The production method according to claim 1, characterized in that the content of the trivalent metal salt in the mixed solution is determined such that the mass of the trivalent metal in the trivalent metal salt is 1% to 10% of the mass of the support.
6. The production method according to claim 1, wherein the volume of the mixed solution is a product of the mass of the carrier and the water absorption rate of the carrier.
7. The production method according to claim 1, wherein in the step (1), the pH of the mixed solution is adjusted to 8 to 10.
8. The method according to claim 1, wherein the divalent metal salt includes at least one of a nitrate of copper, a sulfate of copper, and a chloride of copper, and the trivalent metal salt includes at least one of a nitrate of iron, a sulfate of iron, and a chloride of iron.
9. The method according to claim 1, wherein the organic amine includes at least one of urea, hexamethylenetetramine, cetyltrimethylammonium bromide, and polyacrylamide, and the ammonium salt includes at least one of ammonium carbonate and ammonium bicarbonate.
10. A catalyst produced by the production method according to any one of claims 1 to 9.
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