CN110773235A - Clay-loaded ultra-dispersed metal catalyst for sewage treatment and preparation method thereof - Google Patents
Clay-loaded ultra-dispersed metal catalyst for sewage treatment and preparation method thereof Download PDFInfo
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- CN110773235A CN110773235A CN201911080164.9A CN201911080164A CN110773235A CN 110773235 A CN110773235 A CN 110773235A CN 201911080164 A CN201911080164 A CN 201911080164A CN 110773235 A CN110773235 A CN 110773235A
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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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- 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
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
Abstract
The invention relates to a clay-loaded ultra-dispersed metal catalyst for sewage treatment and a preparation method thereof. Dispersing montmorillonite in water, and adding sodium hydroxide; filtering, washing and drying for later use; dissolving transition metal salt; dissolving or dispersing the pyridine compound in a solvent, and mixing the prepared pyridine compound solution to obtain the transition metal complex. Taking montmorillonite, adding deionized water, adding the metal complex into the montmorillonite suspension, and heating. Filtering, washing, drying and cooling to room temperature. The viscosity reduction rate of the metal catalyst reaches more than 90%, and the Chemical Oxygen Demand (COD) is reduced by more than 95%.
Description
Technical Field
The invention relates to the technical field of oil and gas field pollutant cleaning. In particular to a preparation method of a clay-loaded ultra-dispersed metal catalyst for sewage treatment.
Background
The Fenton oxidation method is a sewage treatment method mainly adopted in the field of oil and gas fields at present and is used for oxidizing and degrading organic matters in the sewage of the oil fields. Fenton reagent is H
2O
2With Fe
2+The formed system has extremely strong oxidizing ability and is an effective system for chemically oxidizing and degrading organic polymers. H
2O
2Under certain conditions, the catalyst can be decomposed to form hydroxyl radical with strong oxidizability, and the oxidation-reduction potential of the hydroxyl radical in water is 2.8V and higher than H
2O
2(1.8V). The hydroxyl radical oxidizes the organic matter into CO through electron transfer and other ways
2And H
2O, and an excess of H
2O
2Can be gradually degraded into H
2O, the mineralization degree of formation fluid cannot be increased, and secondary pollution cannot be caused, so that the method is a clean oxidation system, is already widely applied in the oil field water treatment link at present, and is used for reducing the viscosity of the oil field operation wastewater and removing the Chemical Oxygen Demand (COD). However, although the Fenton system is superior to other systems, the activity of the Fenton reagent is still relatively low and is greatly influenced by external conditions, especially the pH value, and the pH value is more than 3, namely precipitation, so that the Fenton reagent can only be used in a weakly acidic environment. The persulfate is also used for reducing viscosity and COD of the wastewater generated in the oilfield operation, but the persulfate has low activity and incomplete reaction and is difficult to efficiently utilize.
On the other hand, montmorillonite is a non-metal mineral product with montmorillonite as the main mineral component, and the montmorillonite structure is 2: form 1 crystal structure, due to the presence of certain cations, such as Ca, in the layered structure formed by the montmorillonite unit cells
2+、Mg
2+、Na
+、K
+And the function of the cations and montmorillonite unit cells is unstable, and the cations are easy to exchange with other cations, so that the cation has better ion exchange property. Can be used as cation exchange material.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide a preparation method of a clay-supported ultra-dispersed metal catalyst for sewage treatment. Montmorillonite is a clay mineral with montmorillonite as the main mineral component, and the montmorillonite structure is 2: the crystal structure of the type 1 has better ion exchange performance because certain cations, such as Ca, Mg, Na, K and the like, exist in a layered structure formed by montmorillonite unit cells, and the cations have unstable action with the montmorillonite unit cells and are easy to exchange with other cations. More importantly, a plurality of hexagonal cavities are formed in the middle of the crystal faces of the silicon-oxygen tetrahedron in the montmorillonite, and cations can be separated like bowls so as to achieve a highly dispersed state. The invention uses ion exchange of exchangeable cations and transition metal complexes to fix the transition metal complexes on the montmorillonite to form a stable and highly dispersed solid catalyst. The transition metal complex Fenton catalyst is immobilized by montmorillonite, has the characteristics of high efficiency and wide application range of pH value (range from strong acidity to strong basicity), and can effectively degrade organic polymers under mild conditions. In addition, the aluminum hydroxyl on the surface of the montmorillonite can react with strong base to be converted into corresponding meta-aluminate, and the exchange capacity with cations in the solution is also increased.
In order to achieve the purpose, the invention adopts the technical scheme that:
the preparation method of the clay-loaded ultra-dispersed metal catalyst for sewage treatment comprises the following steps:
firstly, dispersing montmorillonite in water with the mass of 5-10 times of that of the montmorillonite at room temperature, uniformly stirring, adding sodium hydroxide with the mass of 5-20% of that of the montmorillonite, and stirring for 2-8 hours, wherein the water and the montmorillonite are products with chemical purity and above purity;
step two, filtering the montmorillonite, washing the montmorillonite to be neutral by using the water used in the step one, and drying the montmorillonite at the temperature of 60-110 ℃ for later use;
thirdly, at room temperature, dissolving transition metal salt in 5-20 times of solvent, wherein the transition metal salt is FeCl with chemical purity and purity higher than chemical purity
2、FeCl
3、Fe
2(SO
4)
3、CoCl
2、NiCl
2、CuCl
2、CuSO
4And ZnCl
2The solvent is water with chemical purity and the purity above,One or more of methanol, ethanol, ethylene glycol and propylene glycol.
And fourthly, dissolving or dispersing another pyridine compound in a solvent which is 5-20 times of the weight of the pyridine compound, wherein the pyridine compound is phenanthroline, pyridine, 2-2 bipyridine, melamine and 4-4 bipyridine which are chemically pure or have higher purity, and the solvent is one or more of water, methanol, ethanol, ethylene glycol and propylene glycol which are chemically pure or have higher purity.
And fifthly, dropwise adding the pyridine compound solution prepared in the fourth step into the solution prepared in the third step according to the mass ratio of the transition metal salt solution to the pyridine compound solution of 1:2-5, and uniformly stirring until the transition metal salt solution and the pyridine compound solution are completely dissolved to obtain the transition metal complex.
Sixthly, taking montmorillonite with the mass of 5-10 times of that of the transition metal salt, adding deionized water with the mass of 5-10 times of that of the montmorillonite, stirring uniformly, adding the metal complex obtained in the fifth step into the montmorillonite suspension dropwise under stirring, heating to 30-80 ℃, and stirring for 2-8 hours.
And seventhly, filtering the mixture, washing with deionized water until no transition metal ions are detected in the third step, drying at 60-105 ℃ for 4-24 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The invention has the beneficial effects that: the catalyst can catalyze hydrogen peroxide or sodium persulfate within the pH range of 1-14 to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution, the viscosity of the aqueous solution before and after reaction is measured by using an Ubbelohde viscometer, and the viscosity reduction rate is more than 90%; under the condition of enough oxidant, the COD can be catalyzed and reduced by more than 92 percent by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Examples
The invention is further illustrated by the following examples. It should be understood that the method described in the examples is only for illustrating the present invention and not for limiting the present invention, and that simple modifications of the preparation method of the present invention based on the concept of the present invention are within the scope of the claimed invention.
The invention is further described with reference to specific examples.
Example 1
Firstly, dispersing montmorillonite in water with the mass 5 times that of the montmorillonite at room temperature, uniformly stirring, adding sodium hydroxide with the mass 5% of that of the montmorillonite, and stirring for 2 hours, wherein the water and the montmorillonite are chemically pure products;
step two, filtering the montmorillonite, washing the montmorillonite to be neutral by using the water used in the step one, and drying the montmorillonite at the temperature of 60 ℃ for later use;
thirdly, at room temperature, dissolving transition metal salt in 5 times of solvent, wherein the transition metal salt is chemically pure FeCl
2The solvent is chemically pure water.
And step four, dissolving another pyridine compound in a solvent which is 20 times of the amount of the pyridine compound, wherein the pyridine compound is chemically pure o-phenanthroline, and the solvent is chemically pure water.
And fifthly, dropwise adding the pyridine compound solution prepared in the fourth step into the solution prepared in the third step according to the mass ratio of the transition metal salt solution to the pyridine compound solution of 1:3, and uniformly stirring until the transition metal salt solution and the pyridine compound solution are completely dissolved to obtain the transition metal complex.
And sixthly, taking montmorillonite with the mass 5 times that of the transition metal salt, adding deionized water with the mass 10 times that of the montmorillonite, uniformly stirring, dropwise adding the metal complex obtained in the fifth step into the montmorillonite suspension under stirring, heating to 80 ℃, and stirring for 2 hours.
And seventhly, filtering the mixture, washing with deionized water until no transition metal ions are detected in the third step, drying at 60 ℃ for 24 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The invention has the beneficial effects that: the catalyst can catalyze hydrogen peroxide to break molecular chains of common oil field polymers such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution when the dosage is 0.1% of glue solution, the pH value is 6, the reaction time is 1h, the viscosity of the 0.5% aqueous solution before and after reaction is measured by an Ubbelohde viscometer, and the viscosity reduction rate is 93%, 96%, 94% and 97% respectively; in the case of sufficient oxidant, COD reductions of 95%, 97%, 99% and 94% were catalysed after the reaction, as determined by the chemical oxygen demand assay of GB 11914-89. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 2
Firstly, dispersing montmorillonite in water with the mass 6 times that of the montmorillonite at room temperature, uniformly stirring, adding sodium hydroxide with the mass 8% of that of the montmorillonite, and stirring for 4 hours, wherein the water and the montmorillonite are chemically pure products;
step two, filtering the montmorillonite, washing the montmorillonite to be neutral by using the water used in the step one, and drying the montmorillonite at 80 ℃ for later use;
thirdly, at room temperature, dissolving a transition metal salt in a solvent of which the concentration is 10 times that of the transition metal salt, wherein the transition metal salt is analytically pure FeCl
3The solvent is chemically pure methanol.
And fourthly, dissolving another pyridine compound in a 15-time solvent, wherein the pyridine compound is chemically pure 2-2 bipyridyl, and the solvent is methanol with chemical purity or higher.
And fifthly, dropwise adding the pyridine compound solution prepared in the fourth step into the solution prepared in the third step according to the mass ratio of the transition metal salt solution to the pyridine compound solution of 1:3.5, and uniformly stirring until the transition metal salt solution and the pyridine compound solution are completely dissolved to obtain the transition metal complex.
And sixthly, taking montmorillonite with the mass 6 times that of the transition metal salt, adding deionized water with the mass 8 times that of the montmorillonite, uniformly stirring, dropwise adding the metal complex obtained in the fifth step into the montmorillonite suspension under stirring, heating to 70 ℃, and stirring for 3 hours, wherein the montmorillonite is industrial-grade sodium-based montmorillonite.
And seventhly, filtering the mixture, washing with deionized water until no transition metal ions are detected in the third step, drying at 75 ℃ for 16 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The catalyst can catalyze sodium persulfate to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution when the dosage is 0.2% of glue solution, the pH value is 7, the temperature is 40 ℃, the reaction time is 1h, the viscosity of the 0.3% aqueous solution before and after reaction is measured by adopting an Ubbelohde viscometer, and the viscosity reduction rates are 92%, 93%, 91% and 93% respectively; in the case of sufficient oxidant, COD reduction of 96%, 95%, 98% and 96% can be catalyzed after the reaction, as determined by GB11914-89 chemical oxygen demand determination. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 3
Firstly, dispersing montmorillonite in water with the mass of 7 times at room temperature, uniformly stirring, adding sodium hydroxide with the mass of 10% of that of the montmorillonite, and stirring for 5 hours, wherein the water and the montmorillonite are analytically pure products;
step two, filtering the montmorillonite, washing the montmorillonite to be neutral by using the water used in the step one, and drying the montmorillonite at 80 ℃ for later use;
thirdly, at room temperature, dissolving a transition metal salt in a solvent 15 times of the transition metal salt, wherein the transition metal salt is analytically pure CoCl
2The solvent is analytically pure ethanol.
And fourthly, dispersing another pyridine compound in a 10-time solvent, wherein the pyridine compound is analytically pure melamine, and the solvent is analytically pure ethanol.
And fifthly, dropwise adding the pyridine compound solution prepared in the fourth step into the solution prepared in the third step according to the mass ratio of the transition metal salt solution to the pyridine compound solution of 1:2.5, and uniformly stirring until the transition metal salt solution and the pyridine compound solution are completely dissolved to obtain the transition metal complex.
And sixthly, taking montmorillonite with the mass being 7 times that of the transition metal salt, adding deionized water with the mass being 8 times that of the montmorillonite, uniformly stirring, dropwise adding the metal complex obtained in the fifth step into the montmorillonite suspension under stirring, heating to 60 ℃, and stirring for 3 hours, wherein the montmorillonite is chemical pure sodium-based montmorillonite.
And seventhly, filtering the mixture, washing with deionized water until no transition metal ions are detected in the third step, drying at 80 ℃ for 12 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The catalyst can catalyze potassium persulfate to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution when the dosage is 0.1% of glue solution, the pH value is 9, the temperature is 50 ℃, the reaction time is 0.2h, the viscosity of the 0.4% aqueous solution before and after reaction is measured by adopting an Ubbelohde viscometer, and the viscosity reduction rate is respectively 97%, 99%, 92% and 95%; under the condition of enough oxidant, the COD can be reduced by 99%, 98% and 99% by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 4
Firstly, dispersing montmorillonite into water with the mass of 8 times at room temperature, uniformly stirring, adding sodium hydroxide with the mass of 12% of that of the montmorillonite, and stirring for 6 hours, wherein the water and the montmorillonite are analytically pure products;
step two, filtering the montmorillonite, washing the montmorillonite to be neutral by using the water used in the step one, and drying the montmorillonite at 90 ℃ for later use;
thirdly, at room temperature, dissolving a transition metal salt into a solvent with the volume 20 times that of the transition metal salt, wherein the transition metal salt is analytically pure NiCl
2The solvent is analytically pure ethanol and glycol with the volume ratio of 1: 1.
And fourthly, dissolving or dispersing another pyridine compound in a 5-time solvent, wherein the pyridine compound is analytically pure pyridine, and the solvent is analytically pure ethanol and glycol with the volume ratio of 1: 1.
And fifthly, dropwise adding the pyridine compound solution prepared in the fourth step into the solution prepared in the third step according to the mass ratio of the transition metal salt solution to the pyridine compound solution of 1:5, and uniformly stirring until the transition metal salt solution and the pyridine compound solution are completely dissolved to obtain the transition metal complex.
And sixthly, taking montmorillonite with the mass of 8 times of that of the transition metal salt, adding deionized water with the mass of 6 times of that of the montmorillonite, uniformly stirring, dropwise adding the metal complex obtained in the fifth step into the montmorillonite suspension under stirring, heating to 50 ℃, and stirring for 5 hours, wherein the montmorillonite is analytically pure calcium-based montmorillonite.
And seventhly, filtering the mixture, washing with deionized water until no transition metal ions are detected in the third step, drying at 100 ℃ for 5 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The catalyst can catalyze hydrogen peroxide to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution when the dosage is 0.4% of glue solution, the pH value is 11, the reaction time is 35 ℃, the viscosity of the 0.3% aqueous solution before and after reaction is measured by adopting an Ubbelohde viscometer, and the viscosity reduction rate is respectively 96%, 94%, 95% and 98%; under the condition of sufficient oxidant, COD can be reduced by 97%, 98% and 99% by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 5
Firstly, dispersing montmorillonite in water with the mass of 9 times at room temperature, uniformly stirring, adding sodium hydroxide with the mass of 15% of that of the montmorillonite, and stirring for 8 hours, wherein the water and the montmorillonite are chemically pure products;
step two, filtering the montmorillonite, washing the montmorillonite to be neutral by using the water used in the step one, and drying the montmorillonite for later use at 100 ℃;
thirdly, at room temperature, dissolving a transition metal salt in a solvent of which the volume is 10 times that of the transition metal salt, wherein the transition metal salt is chemically pure CuCl
2The solvent is chemically pure methanol and propylene glycol with the volume ratio of 2: 1.
And fourthly, dissolving another pyridine compound in a 5-time solvent, wherein the pyridine compound is chemically pure 4-4 bipyridyl, and the solvent is chemically pure methanol and propylene glycol in a volume ratio of 2: 1.
And fifthly, dropwise adding the pyridine compound solution prepared in the fourth step into the solution prepared in the third step according to the mass ratio of the transition metal salt solution to the pyridine compound solution of 1:2.8, and uniformly stirring until the transition metal salt solution and the pyridine compound solution are completely dissolved to obtain the transition metal complex.
And sixthly, taking montmorillonite with the mass 6 times that of the transition metal salt, adding deionized water with the mass 8 times that of the montmorillonite, uniformly stirring, dropwise adding the metal complex obtained in the fifth step into the montmorillonite suspension under stirring, heating to 40 ℃, and stirring for 7 hours, wherein the montmorillonite is chemical pure sodium-based montmorillonite.
And seventhly, filtering the mixture, washing with deionized water until no transition metal ions are detected in the third step, drying at 105 ℃ for 4 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The catalyst can catalyze hydrogen peroxide to break molecular chains of common oil field polymers such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution when the dosage is 0.2% of glue solution, the pH value is 10, the temperature is 30 ℃, the reaction time is 2 hours, the viscosity of the 0.4% aqueous solution before and after reaction is measured by adopting an Ubbelohde viscometer, and the viscosity reduction rate is 99%, 99% and 99% respectively; under the condition of enough oxidant, the COD can be reduced by 98%, 97%, 98% and 99% by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 6
Firstly, dispersing montmorillonite into water with the mass of 10 times at room temperature, uniformly stirring, adding sodium hydroxide with the mass of 20% of that of the montmorillonite, and stirring for 8 hours, wherein the water and the montmorillonite are chemically pure products;
step two, filtering the montmorillonite, washing the montmorillonite to be neutral by using the water used in the step one, and drying the montmorillonite for later use at 110 ℃;
thirdly, at room temperature, dissolving a transition metal salt in a solvent of which the volume is 5 times that of the transition metal salt, wherein the transition metal salt is chemically pure ZnCl
2The solvent is chemically pure water.
And step four, dissolving another pyridine compound in a solvent which is 5 times of the amount of the pyridine compound, wherein the pyridine compound is chemically pure o-phenanthroline, and the solvent is chemically pure.
And fifthly, dropwise adding the pyridine compound solution prepared in the fourth step into the solution prepared in the third step according to the mass ratio of the transition metal salt solution to the pyridine compound solution of 1:3, and uniformly stirring until the transition metal salt solution and the pyridine compound solution are completely dissolved to obtain the transition metal complex.
And sixthly, taking montmorillonite with the mass being 10 times of that of the transition metal salt, adding deionized water with the mass being 10 times of that of the montmorillonite, uniformly stirring, dropwise adding the metal complex obtained in the fifth step into the montmorillonite suspension under stirring, heating to 300 ℃, and stirring for 8 hours, wherein the montmorillonite is chemically pure calcium-based montmorillonite.
And seventhly, filtering the mixture, washing with deionized water until no transition metal ions are detected in the third step, drying at 60 ℃ for 24 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The catalyst can catalyze hydrogen peroxide to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution when the dosage is 0.5% of glue solution, the pH value is 14, the reaction time is 40 ℃, the viscosity of the 0.6% aqueous solution before and after reaction is measured by adopting an Ubbelohde viscometer, and the viscosity reduction rate is 99%, 98% and 99% respectively; under the condition of enough oxidant, the COD can be reduced by 99%, 98% and 99% by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Claims (7)
1. A composition characterized by comprising the following components: montmorillonite, transition metal complexes; wherein the mass of the montmorillonite is 5-10 times of that of the transition metal.
2. The composition of claim 1, wherein: the transition metal complex is formed by a transition metal salt and a pyridine compound; the transition metal salt is selected from FeCl with chemical purity and purity above
2、FeCl
3、Fe
2(SO
4)
3、CoCl
2、NiCl
2、CuCl
2、CuSO
4And ZnCl
2One or more of the above; the pyridine compound is one or more selected from phenanthroline, pyridine, 2-2 bipyridine, melamine and 4-4 bipyridine with chemical purity or higher.
3. The composition of claim 1, wherein: the montmorillonite is industrial calcium-based montmorillonite and/or sodium-based montmorillonite.
4. A process for preparing a composition according to any one of claims 1 to 3, characterized in that:
1) dispersing montmorillonite in water of 5-10 times of the mass of the montmorillonite at room temperature, stirring uniformly, adding sodium hydroxide of 5-20% of the mass of the montmorillonite, and stirring for 2-8 hours, wherein the water and the montmorillonite are products of chemical purity and above;
2) filtering the montmorillonite, washing with the water used in the step 1) to be neutral, and drying at 60-110 ℃ for later use;
3) dissolving transition metal salt in 5-20 times of solvent at room temperature, wherein the transition metal salt is selected from FeCl with chemical purity and purity higher than chemical purity
2、FeCl
3、Fe
2(SO
4)
3、CoCl
2、NiCl
2、CuCl
2、CuSO
4And ZnCl
2One or more of the above; the solvent is one or more of water, methanol, ethanol, ethylene glycol and propylene glycol with chemical purity or higher.
4) Dissolving or dispersing pyridine compounds in a solvent of which the amount is 5-20 times that of the pyridine compounds, wherein the pyridine compounds are selected from one or more of phenanthroline, pyridine, 2-2 bipyridyl, melamine and 4-4 bipyridyl which are chemically pure and have the above purity; the solvent is one or more of water, methanol, ethanol, ethylene glycol and propylene glycol with chemical purity or higher.
5) Dropwise adding the pyridine compound solution prepared in the step 4) into the solution prepared in the step 3) according to the mass ratio of the transition metal salt solution to the pyridine compound solution of 1:2-5, and uniformly stirring until the transition metal salt solution and the pyridine compound solution are completely dissolved to obtain a transition metal complex;
6) taking montmorillonite with 5-10 times mass of transition metal salt, adding deionized water with 5-10 times mass of montmorillonite, stirring uniformly, adding the metal complex obtained in step 5) into the montmorillonite suspension dropwise under stirring, heating to 30-80 ℃, and stirring for 2-8 hours.
7) And (3) filtering the mixture, washing with deionized water until the transition metal ions are not detected in the step 3), drying at 60-105 ℃ for 4-24 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
5. A composition characterized by being prepared by the method of claim 4.
6. A supported ultra-dispersed metal catalyst characterized by comprising the composition of any one of claims 1 to 3, and an auxiliary therefor.
7. Use of the composition of any one of claims 1 to 3 or claim 5, the catalyst of claim 6 in petrochemical industry; preferably, the application in the aspects of catalyzing hydrogen peroxide and persulfate to oxidize and degrade high molecular polymers for oilfield operation and treating industrial wastewater of the oilfield.
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