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CN111068761A - Wet oxidation catalyst and organic wastewater treatment method - Google Patents

Wet oxidation catalyst and organic wastewater treatment method Download PDF

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Publication number
CN111068761A
CN111068761A CN201811214060.8A CN201811214060A CN111068761A CN 111068761 A CN111068761 A CN 111068761A CN 201811214060 A CN201811214060 A CN 201811214060A CN 111068761 A CN111068761 A CN 111068761A
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Prior art keywords
parts
weight
catalyst
hours
carrier
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CN201811214060.8A
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Chinese (zh)
Inventor
郑育元
陈航宁
郭宗英
许丹丹
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to CN201811214060.8A priority Critical patent/CN111068761A/en
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • 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
    • C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • C02F2103/06—Contaminated groundwater or leachate

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a wet oxidation catalyst and an organic wastewater treatment method, and mainly solves the problem of low COD removal rate in the prior art. The invention adopts a wet oxidation catalyst which comprises the following components, by weight, a) 65.0-85.0 parts of carrier, and b) 15.0-35.0 parts of active element loaded on the carrier; the active element comprises at least one of the substances consisting of Fe, Cu, Co, Mn, Ni and Zn, thereby better solving the problem and being applicable to the treatment of organic wastewater.

Description

Wet oxidation catalyst and organic wastewater treatment method
Technical Field
The invention relates to a wet oxidation catalyst and an organic wastewater treatment method.
Background
Wet oxidation is a method for treating toxic, harmful and high-concentration organic wastewater by adopting simple substance-oxygen under the condition of high pressure and high temperature, which is developed in the last 50 th century. In the 70 s of the 20 th century, catalytic wet oxidation was developed on the basis of wet oxidation, so that the wastewater treatment efficiency was improved, and the reaction conditions were reduced. The catalytic wet oxidation technology can be used for independently treating wastewater and can also be used as pretreatment of biochemical treatment, the COD of the wastewater is reduced through wet oxidation, toxic and harmful substances to biochemical bacteria are removed, and the biodegradability of the wastewater is improved. On the other hand, along with the pressure of energy saving and consumption reduction is continuously increased, the environmental protection control is more and more strict, the waste water with higher organic matter concentration adopts the incinerator incineration treatment to cause energy consumption and environmental protection dual pressure for the device, the catalytic wet oxidation technology can replace the waste water incinerator to a great extent, the energy consumption is reduced, and the device waste water treatment meets the environmental protection requirement.
The catalytic wet oxidation technology is classified into homogeneous and heterogeneous catalytic wet oxidation according to the properties of the catalyst. Early studies focused primarily on homogeneous catalysts, but this process was phased out because of the secondary pollution caused by the catalyst dissolving in the waste, requiring subsequent treatment. In recent years, heterogeneous catalysts have become a focus of research, and the heterogeneous catalysts mainly include two main types, namely noble metals and metal oxides, wherein the metal oxide supported catalysts are mostly TiO2、Al2O3、SiO2、ZrO2Or a composite oxide thereof as a carrier, and an excess element such as Cu, Co, Mn, Fe, Ni, or the like is supported on the carrier. However, since the stability of the catalyst is poor due to the fact that the active elements are easily dissolved out, improvement of the prior art is needed.
The following patents are published for metal oxide catalytic wet oxidation technology:
CN101844827B discloses a catalyst for degrading high-concentration formaldehyde pollutants, which is prepared by loading transition metal components (one of Cu, Ni, Fe, Mn, Co and Zn) and rare earth elements on AlO2、SiO2Or TiO2The preparation technology of the impregnation method is adopted. CN101219376B discloses a catalyst for wastewater treatment, which is prepared from gamma-Al2O3Mn metal oxide as a carrier, Sn metal oxide as a main active component and Sb oxide as an auxiliary agent. CN101485987B belongs to the field of water treatment technology and environmental functional materials,the catalyst is prepared by taking powdery zinc-aluminum hydrotalcite as a carrier, Fe as an active component and Ce and Ti as promoters by a layered impregnation method.
Disclosure of Invention
The invention aims to solve the technical problem that the removal rate of COD (chemical oxygen demand) in the heterogeneous catalytic wet oxidation reaction in the prior art is low, and provides a novel wet oxidation catalyst. The catalyst is used for treating organic wastewater and has the advantage of high COD removal rate.
The second technical problem to be solved by the present invention is to provide a method for preparing the catalyst corresponding to the first technical problem.
The present invention is also directed to a method for treating organic wastewater using the catalyst for solving one of the problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
the wet oxidation catalyst comprises the following components in parts by weight:
a)65.0 to 85.0 parts of carrier, and carrier supported thereon
b) 15.0-35.0 parts of active elements;
the active element includes at least one selected from the group consisting of Fe, Cu, Co, Mn, Ni, and Zn.
The technical key of the invention is the choice of the active ingredient, as far as the carrier is concerned, it is reasonable and without inventive effort for the person skilled in the art to choose. For example, but not limited to, the carrier includes at least one selected from the group consisting of ZSM-5 molecular sieves, MCM-41 molecular sieves, diatomaceous earth and hydrotalcite.
In the above technical solution, the active elements preferably include both a main active element and an auxiliary active element, the main active element includes Fe, and the auxiliary active element includes at least one selected from a group of substances consisting of Co, Mn, and Ni. The main active elements and the auxiliary active elements have a synergistic effect in improving the COD removal efficiency. At this time, the ratio of the primary active element to the auxiliary active element is not particularly limited as long as a comparable synergistic effect can be obtained by simultaneously including the primary active element and the auxiliary active element. By way of non-limiting example, the mass ratio of the primary active element to the secondary active element may be 1.5 to 10, and within this mass ratio, non-limiting specific point values may be, for example, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, and so forth.
In the technical scheme, the active elements simultaneously comprise Co and Mn, and the Co and Mn have a synergistic effect on the aspect of removing COD (chemical oxygen demand) of the organic wastewater. The ratio of Co to Mn is not particularly limited, and any ratio can achieve a comparable synergistic effect if Co and Mn are included at the same time. The mass ratio of Co to Mn may be, by way of non-limiting example, 0.1 to 10, and within this mass ratio, non-limiting specific values may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 4.5, 5, 6, 7, 8, 9, and the like.
In the technical scheme, the active elements simultaneously comprise Ni and Mn, and the Ni and the Mn have a synergistic effect on the aspect of removing COD (chemical oxygen demand) of the organic wastewater. The ratio of Ni to Mn is not particularly limited, and any ratio can achieve a comparable synergistic effect if Ni and Mn are included at the same time. As a non-limiting example, the mass ratio of Ni to Mn may be 0.1 to 10, and within this mass ratio, non-limiting specific values may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 4.5, 5, 6, 7, 8, 9, and the like.
In the technical scheme, the active elements simultaneously comprise Co and Ni, and the Co and the Ni have a synergistic effect on the aspect of removing COD (chemical oxygen demand) of the organic wastewater. The ratio of Co to Ni is not particularly limited, and any ratio can achieve a comparable synergistic effect if Co and Ni are included at the same time. As a non-limiting example, the mass ratio of Co to Ni may be 0.1 to 10, and within this mass ratio, non-limiting specific point values may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 4.5, 5, 6, 7, 8, 9, and the like.
In the technical scheme, the carriers preferably comprise an MCM-41 molecular sieve and a ZSM-5 molecular sieve at the same time, and the combination of the two carriers has a synergistic effect on the removal of COD (chemical oxygen demand) of the organic wastewater. The ratio of the MCM-41 molecular sieve to the ZSM-5 molecular sieve is not particularly limited as long as any ratio of the carrier including both the MCM-41 molecular sieve and the ZSM-5 molecular sieve can achieve comparable synergistic effects. By way of non-limiting example, the mass ratio of the MCM-41 molecular sieve to the ZSM-5 molecular sieve may be 0.1 to 10, and within this mass ratio range, non-limiting specific values may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 4.5, 5, 6, 7, 8, 9, and so forth.
To solve the second technical problem, the technical solution of the present invention is as follows: the process for the preparation of the catalyst according to any of the preceding technical solutions, comprising the steps of:
1) mixing the carrier powder and a binder, molding, drying and roasting to obtain a molded carrier;
2) and mixing the formed carrier with the solution of the active element, drying and roasting to obtain the catalyst.
In the above technical scheme, the particle size of the powder of the carrier is not particularly limited, and it can be understood that the finer the powder, the more uniform the subsequent mixing. It is used. For example but not limited to MCM-41 powder with average particle size of 0.5-10 μm, and for example but not limited to ZSM-5 molecular sieve powder with average particle size of 0.5-5 μm.
The preparation method of the catalyst support of the present invention is not particularly limited, such as but not limited to: tabletting, rolling ball forming, extruding and forming, etc., wherein the used adhesive can be organic adhesive (including PEG, CMC, methylcellulose, starch, etc.) or inorganic adhesive (including nitric acid, aluminum sol, silica sol, etc.).
In the technical scheme, the roasting temperature in the step 1) is 400-600 ℃, more preferably 450-550 ℃, and the roasting time is preferably 4.0-4.4 h.
In the technical scheme, the roasting temperature in the step 2) is 300-500 ℃, more preferably 350-450 ℃, and the roasting time is preferably 4.5-5.5 h.
To solve the third technical problem, the technical scheme of the invention is as follows: a method for treating organic wastewater, comprising, in the presence of the catalyst according to any one of the preceding technical problems, contacting organic wastewater with an oxygen-containing oxidant to react and remove COD.
In the above technical solution, as a non-limiting example, the organic wastewater may be but is not limited to landfill leachate, industrial acrylic acid wastewater, printing wastewater, and the like, and all can achieve comparable technical effects. For the same reason, the embodiment of the invention generally adopts the landfill leachate.
The technical key of the present invention is the choice of catalyst, once the catalyst is determined, the skilled person can reasonably choose the process conditions to be used, such as but not limited to:
the reaction temperature is 220-300 ℃, and more preferably 240-280 ℃.
The reaction pressure is 5.0 to 10.0MPa, and more preferably 6.0 to 9.0 MPa.
The volume ratio of the oxygen to the organic wastewater can be 50-400.
The mass airspeed of the organic wastewater can be 0.4-1.2 h-1。
The evaluation method of the catalyst of the present invention is as follows: 100g of catalyst is taken and loaded into a wet oxidation reactor (the reactor is a fixed bed reactor, the inner diameter is 22mm, the length of the reactor is 700mm), landfill leachate with the COD value of 25000mg/l is taken as a raw material, and the raw material is mixed with oxygen and then passes through the wet oxidation reactor filled with the catalyst. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. Time is used as an indicator of stability, with longer times indicating more stable catalyst.
By adopting the technical scheme of the invention, the landfill leachate and oxygen are mixed and then pass through a wet oxidation reactor filled with a catalyst, the catalyst comprises 20 parts of active components and 80 parts of MCM-41 and ZSM-5 composite carriers in parts by weight, and after reaction for 500 hours at the reaction temperature of 270 ℃, the pressure of 7.5MPa and the volume ratio of the oxygen to the landfill leachate of 200, the highest COD removal rate can reach 99.1 percent, thereby obtaining better technical effects.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Detailed Description
[ example 1 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of the spherical carrier was mixed with 110 parts by weight of an aqueous ferric nitrate solution containing 20 parts by weight of Fe, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 2 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of the spherical carrier and 110 parts by weight of an aqueous cobalt nitrate solution containing 20 parts by weight of Co were mixed, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 3 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of the spherical carrier was mixed with 110 parts by weight of an aqueous manganese nitrate solution containing 20 parts by weight of Mn, allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 4 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of the spherical carrier and 110 parts by weight of nickel nitrate aqueous solution containing 20 parts by weight of Ni were mixed, and the mixture was allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 5 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of the spherical carrier was mixed with 110 parts by weight of an iron nitrate-cobalt nitrate mixed aqueous solution (containing 14 parts by weight of Fe and 6 parts by weight of Co), allowed to stand at room temperature for 4 hours, then dried in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 6 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of the spherical carrier was mixed with 110 parts by weight of an iron nitrate-manganese nitrate mixed aqueous solution (containing 14 parts by weight of Fe and 6 parts by weight of Mn), allowed to stand at room temperature for 4 hours, then dried in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 7 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of the spherical carrier was mixed with 110 parts by weight of an iron nitrate-nickel nitrate mixed aqueous solution (containing 14 parts by weight of Fe and 6 parts by weight of Ni), allowed to stand at room temperature for 4 hours, then dried in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 8 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of the spherical carrier was mixed with 110 parts by weight of an iron nitrate-cobalt nitrate-manganese nitrate mixed aqueous solution (containing 14 parts by weight of Fe, 3 parts by weight of Co and 3 parts by weight of Mn), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 9 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of the spherical carrier was mixed with 110 parts by weight of an iron nitrate-cobalt nitrate-nickel nitrate mixed aqueous solution (containing 14 parts by weight of Fe, 3 parts by weight of Co and 3 parts by weight of Ni), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of catalyst is taken and loaded into a wet oxidation fixed bed reactorThe reaction is carried out in a reactor. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 10 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of the spherical carrier was mixed with 110 parts by weight of an iron nitrate-manganese nitrate-nickel nitrate mixed aqueous solution (containing 14 parts by weight of Fe, 3 parts by weight of Mn and 3 parts by weight of Ni), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 11 ]
1. Preparation of the support
80 parts by weight of MCM-41 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball shape, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of a spherical carrier was mixed with 110 parts by weight of a mixed aqueous solution of iron nitrate-cobalt nitrate-manganese nitrate-nickel nitrate (containing 14 parts by weight of Fe, 2 parts by weight of Co, 2 parts by weight of Mn and 2 parts by weight of Ni), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 12 ]
1. Preparation of the support
80 parts by weight of ZSM-5 powder (average particle diameter of 1 μm) was put into a kneader and mixed, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneaded, extruded, rolled into a ball, dried at 100 ℃ for 12 hours, and then calcined at 450 ℃ for 4.2 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of a spherical carrier was mixed with 110 parts by weight of a mixed aqueous solution of iron nitrate-cobalt nitrate-manganese nitrate-nickel nitrate (containing 14 parts by weight of Fe, 2 parts by weight of Co, 2 parts by weight of Mn and 2 parts by weight of Ni), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 13 ]
1. Preparation of the support
40 parts by weight of MCM-41 powder (average particle size of 1 μm) and 40 parts by weight of ZSM-5 powder (average particle size of 1 μm) were mixed in a kneader, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneading, bar-extruding, ball-rolling molding were carried out, drying was carried out at 100 ℃ for 12 hours, and then baking was carried out at 450 ℃ for 4.2 hours, to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of a spherical carrier was mixed with 110 parts by weight of a mixed aqueous solution of iron nitrate-cobalt nitrate-manganese nitrate-nickel nitrate (containing 14 parts by weight of Fe, 2 parts by weight of Co, 2 parts by weight of Mn and 2 parts by weight of Ni), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 14 ]
1. Preparation of the support
60 parts by weight of MCM-41 powder (average particle size of 1 μm) and 20 parts by weight of ZSM-5 powder (average particle size of 1 μm) were mixed in a kneader, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneading, bar-extruding, ball-rolling molding were carried out, drying was carried out at 100 ℃ for 12 hours, and then baking was carried out at 450 ℃ for 4.2 hours, to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of a spherical carrier was mixed with 110 parts by weight of a mixed aqueous solution of iron nitrate-cobalt nitrate-manganese nitrate-nickel nitrate (containing 14 parts by weight of Fe, 2 parts by weight of Co, 2 parts by weight of Mn and 2 parts by weight of Ni), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, and the oxygen and the landfill leachateThe volume ratio of the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
[ example 15 ]
1. Preparation of the support
20 parts by weight of MCM-41 powder (average particle size of 1 μm) and 60 parts by weight of ZSM-5 powder (average particle size of 1 μm) were mixed in a kneader, 2.4 parts by weight of methylcellulose and 80 parts by weight of water were poured, kneading, bar-extruding, ball-rolling molding were carried out, drying was carried out at 100 ℃ for 12 hours, and then baking was carried out at 450 ℃ for 4.2 hours, to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
80 parts by weight of a spherical carrier was mixed with 110 parts by weight of a mixed aqueous solution of iron nitrate-cobalt nitrate-manganese nitrate-nickel nitrate (containing 14 parts by weight of Fe, 2 parts by weight of Co, 2 parts by weight of Mn and 2 parts by weight of Ni), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation fixed bed reactor and reacted. The reaction temperature is 270 ℃, the pressure is 7.5MPa, the volume ratio of oxygen to the landfill leachate is 200, and the mass airspeed of the landfill leachate is 0.8h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value.
The composition of the catalyst active components is shown in Table 1, and the catalyst evaluation results are shown in Table 2.
TABLE 1
(parts by weight)
Figure BDA0001833106780000131
TABLE 2
Figure BDA0001833106780000141

Claims (10)

1. The wet oxidation catalyst comprises the following components in parts by weight:
a)65.0 to 85.0 parts of carrier, and carrier supported thereon
b) 15.0-35.0 parts of active elements;
the active element includes at least one selected from the group consisting of Fe, Cu, Co, Mn, Ni, and Zn.
2. The catalyst according to claim 1, wherein the carrier comprises at least one selected from the group consisting of ZSM-5 molecular sieves, MCM-41 molecular sieves, diatomaceous earth and hydrotalcite.
3. A method for preparing the catalyst of claim 1, comprising the steps of:
1) mixing the carrier and the binder, molding, drying and roasting to obtain a molded carrier;
2) and mixing the formed carrier with the solution of the active element, drying and roasting to obtain the catalyst.
4. The method according to claim 3, wherein the calcination temperature in the step 1) is 400 to 600 ℃.
5. The method according to claim 3, wherein the calcination temperature in the step 2) is 300 to 500 ℃.
6. A method for treating organic waste water, comprising contacting organic waste water with an oxygen-containing oxidizing agent in the presence of the catalyst according to claim 1 or 2 to remove COD.
7. The treatment method according to claim 6, characterized in that the organic wastewater is landfill leachate.
8. The process of claim 6 wherein the oxidant is oxygen or air.
9. The process according to claim 6, wherein the reaction temperature is 220 to 300 ℃.
10. The process according to claim 6, wherein the reaction pressure is 5.0 to 10.0 MPa.
CN201811214060.8A 2018-10-18 2018-10-18 Wet oxidation catalyst and organic wastewater treatment method Pending CN111068761A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011224550A (en) * 2010-03-30 2011-11-10 Nippon Shokubai Co Ltd Catalyst for treating nitrogen-containing compound, and method of treating waste water using the same
CN107282085A (en) * 2016-04-13 2017-10-24 中国石油化工股份有限公司 Waste water wet oxidizing catalyst
CN107866260A (en) * 2016-09-26 2018-04-03 中国石油化工股份有限公司 The catalyst of wet oxidation waste water

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011224550A (en) * 2010-03-30 2011-11-10 Nippon Shokubai Co Ltd Catalyst for treating nitrogen-containing compound, and method of treating waste water using the same
CN107282085A (en) * 2016-04-13 2017-10-24 中国石油化工股份有限公司 Waste water wet oxidizing catalyst
CN107866260A (en) * 2016-09-26 2018-04-03 中国石油化工股份有限公司 The catalyst of wet oxidation waste water

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陆晓华 等: "《环境污染控制原理》", 28 February 2010, 华中科技大学出版社 *

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