CN107282040B - Heterogeneous catalytic wet oxidation catalyst - Google Patents

Heterogeneous catalytic wet oxidation catalyst Download PDF

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Publication number
CN107282040B
CN107282040B CN201610225965.XA CN201610225965A CN107282040B CN 107282040 B CN107282040 B CN 107282040B CN 201610225965 A CN201610225965 A CN 201610225965A CN 107282040 B CN107282040 B CN 107282040B
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catalyst
cod
wet oxidation
carrier
drying
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CN107282040A (en
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郑育元
陈航宁
郭宗英
吴粮华
顾松园
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • 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
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds

Abstract

The invention relates to a heterogeneous catalysis wet oxidation catalyst, a preparation method and application thereof, and mainly solves the problem of low COD removal rate in the prior art. The invention adopts a heterogeneous catalysis wet oxidation catalyst, which comprises the following components in parts by weight: a)98.0 to 99.8 parts of carrier and loaded thereon, b)0.2 to 2.0 parts of at least one selected from Ru, Pd, Pt and Rh; the carrier is selected from at least one of silicon dioxide, aluminum oxide, titanium oxide, multi-walled carbon nano-tubes and graphite, so that the problem is solved well, and the method can be used for treating industrial acrylonitrile wastewater.

Description

Heterogeneous catalytic wet oxidation catalyst
Technical Field
The invention relates to a heterogeneous catalytic wet oxidation catalyst, a preparation method and application thereof.
Background
Due to the characteristics of water (such as no toxicity, low price, wide sources and the like), the water is often used as a reaction solvent, a medium or a heat carrier in the chemical production process, and therefore, the water quality of a water body is inevitably damaged. With the vigorous development of the chemical industry, the water pollution is on the trend of rising year by year, wherein the water pollution caused by toxic organic matters is particularly serious. The pollutants have the characteristics of large discharge amount, wide pollution range, difficult biodegradation and the like, seriously threaten human life and simultaneously restrict the development of the chemical industry. Therefore, the research on how to treat industrial organic wastewater with high efficiency and energy saving is a problem to be solved urgently.
Industrial waste ofThe water treatment method has special application range. The traditional biological treatment technology, photocatalysis and wet peroxide oxidation are only suitable for treating low-concentration and non-biotoxic organic wastewater. Although the incineration method can treat high-concentration organic wastewater, a large amount of fuel oil is consumed for incineration, and the energy consumption is high; at the same time, incineration may generate, for example, NOx、COxAnd harmful gases such as dioxin cause secondary pollution to the environment. Wet oxidation was developed in the last 50 th century as a method for treating toxic, harmful, high-concentration organic wastewater. The method is to oxidize organic pollutants into CO in liquid phase by taking air or pure oxygen as an oxidant under the conditions of high temperature and high pressure2And inorganic substances such as water and the like or small molecular organic substances. The method has the advantages of wide application range, high treatment efficiency, high oxidation rate, small occupied area of equipment and the like. The catalytic wet oxidation technology is to add a high-efficiency and stable catalyst designed for the composition of wastewater in the traditional wet oxidation process, thereby greatly improving the oxidation efficiency, shortening the reaction residence time, reducing the temperature and pressure required by the reaction and reducing the production cost.
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 research focus, and mainly comprise two main types of noble metals and metal oxides, wherein noble metal supported catalysts have high catalytic activity and stability, and at present, most of such catalysts are TiO2、ZrO2、CeO2Or a composite oxide thereof as a carrier, and Ru, Rh, Pd, Ir, Pt, Au being supported on the carrier. However, the dispersion uniformity of the noble metal is always a difficult point of research on the catalyst, and the improvement of the prior art is needed.
The following patents are published for noble metal catalytic wet oxidation technology:
CN1084496A discloses a wet oxidation purification catalyst for industrial sewage containing high-concentration organic matters and ammonia, which is prepared from noble metal components (Ru, Rh, Cu, Ni, Cu,one of Pd, Ir and Pt) and rare earth element supported on TiO2The preparation method adopts the preparation technology of co-impregnation or sub-impregnation of double active components. CN1121322A discloses a catalyst for wastewater treatment, a method for producing the same, and a method for wastewater treatment using the same, wherein the catalyst contains an oxide and/or composite oxide of manganese and an oxide and/or composite oxide of at least one metal selected from the group consisting of iron, titanium, and zirconium, and optionally a noble metal.
The activity of the catalyst in the above patents is not ideal when the catalyst is used for treating acrylonitrile waste water.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low removal rate of COD in the heterogeneous catalytic wet oxidation reaction in the prior art, and a novel heterogeneous catalytic wet oxidation catalyst is provided. The catalyst is used for treating acrylonitrile wastewater by heterogeneous catalytic wet oxidation reaction, and has the advantages of high COD removal rate and high catalyst strength.
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 invention aims to solve the technical problem and provides a method for treating industrial wastewater by using a catalyst used for solving one of the technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the heterogeneous catalysis wet oxidation catalyst comprises the following components in parts by weight:
a)98.0 to 99.8 parts of carrier, and carrier supported thereon
b) 0.2-2.0 parts of at least one selected from Ru, Pd, Pt and Rh;
the carrier is selected from at least one of silicon dioxide, aluminum oxide, titanium oxide, multi-walled carbon nanotubes (MWCNTs for short) and graphite.
In the above technical solution, the carrier may further include a complex of multi-walled carbon nanotubes and graphite, and research shows that the carrier has an interaction promoting effect in improving the COD removal rate.
In the technical scheme, the mass ratio of the multi-wall carbon nanotubes to the graphite in the composite body is preferably 1: 4-4: 1.
To solve the second technical problem, the technical solution of the present invention is as follows: the preparation method of the catalyst in the technical scheme of one of the technical problems comprises the following steps:
1) mixing the required carrier powder and a binder, extruding and molding, and drying;
2) loading the solution I on a carrier by adopting an impregnation method, drying, and roasting at 350-600 ℃ for 1.5-5.0 h to prepare a catalyst precursor;
3) reducing the catalyst precursor with hydrogen at 300-500 ℃ for 2.5-5 h to obtain the catalyst;
the solution I is prepared by at least one salt selected from Ru, Pd, Pt and Rh and an organic solvent.
In the above technical solution, the organic solvent is selected from at least one of methanol, ethanol, n-propanol and isopropanol.
In the above technical solution, the particle size of the carrier powder is not particularly limited, for example, but not limited to, 10 to 100 μm, and further 10 to 50 μm.
The preparation method of the catalyst support is not particularly limited, such as but not limited to: tablet forming, rolling ball forming, extrusion molding and the like.
The binder is not particularly limited, and those commonly used in the art, such as but not limited to inorganic binders such as silica sol, alumina sol, titanium sol, etc., or cellulose and its derivatives, starch and its derivatives, polyethylene glycol (PEG for short) 200-1000, etc., may be used.
In the technical scheme, the roasting temperature in the step 2) is preferably 400-550 ℃, and the roasting time in the step 2) is preferably 2-4.5 h.
In the technical scheme, the reduction temperature in the step 3) is preferably 350-450 ℃, and the reduction time is preferably 3.0-4.5 h.
To solve the third technical problem, the technical scheme of the invention is as follows: a process for treating the waste water generated in the process of preparing acrylonitrile by oxidizing propylene or propane with ammonia features that the industrial waste water is mixed with oxygen and then reacted in wet oxidizing reactor containing catalyst.
In the technical scheme, the reaction temperature is preferably 220-300 ℃.
In the technical scheme, the reaction pressure is preferably 5.0-10.0 MPa.
In the technical scheme, the volume ratio of the oxygen to the industrial wastewater is preferably 50-400.
In the technical scheme, the mass airspeed of the industrial wastewater is preferably 0.5-1.5 h-1。
The evaluation method of the catalyst of the present invention is as follows: the reactor is a fixed bed reactor, the inner diameter is 14mm, and the length of the reactor is 650 mm. Acrylonitrile industrial wastewater with COD value of 30000mg/l is taken as a raw material, mixed with oxygen and then passes through a wet oxidation reactor filled with a catalyst. The amount of oxidant consumed in the chemical oxidation process of the substances capable of being oxidized in the water body under the specified conditions is expressed by the milligrams of oxygen consumed per liter of water sample, and is called COD (chemical oxygen demand).
By adopting the technical scheme of the invention, the industrial wastewater and oxygen are mixed and then pass through a wet oxidation reactor filled with a catalyst, the catalyst comprises 1 part of Ru and 99 parts of MWCNTs and graphite powder composite carrier in parts by weight, the reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of the oxygen to the industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1Under the condition of (2), the COD removal rate can reach up to 99.0%. Compared with other technologies, the COD removal rate is at least improved by 8.1 percent, and a better technical effect is achieved.
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
And (2) putting 110g of finished MWCNTs powder (with the particle size of 30 mu m) and 110g of finished graphite powder (with the particle size of 30 mu m) into a kneader for mixing, pouring 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water, kneading, extruding, rolling ball forming, and drying at 100 ℃ for 12 hours to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of RuCl containing 2gRu3The methanol solutions were mixed and impregnated. Standing at room temperature for 6h, then drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 450 ℃ for 2.5h to obtain the catalyst precursor. At 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ example 2 ]
1. Preparation of the support
Mixing 132g of finished MWCNTs powder (with the particle size of 30 mu m) and 88g of finished graphite powder (with the particle size of 30 mu m) in a kneader, pouring 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water, kneading, extruding, rolling ball forming, and drying at 100 ℃ for 12 hours to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of RuCl containing 2gRu3The methanol solutions were mixed and impregnated. Standing at room temperature for 6h, then drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 450 ℃ for 2.5h to obtain the catalyst precursor. At 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃ and the pressure9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ example 3 ]
1. Preparation of the support
88g of finished MWCNTs powder (with the particle size of 30 mu m) and 132g of finished graphite powder (with the particle size of 30 mu m) are put into a kneader to be mixed, 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water are poured, kneading, extruding, rolling ball forming are carried out, and drying is carried out at 100 ℃ for 12 hours, so as to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of RuCl containing 2gRu3The methanol solutions were mixed and impregnated. Standing at room temperature for 6h, then drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 450 ℃ for 2.5h to obtain the catalyst precursor. At 400 ℃ in H2-N2Reducing for 4H in an atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ example 4 ]
1. Preparation of the support
And (2) putting 110g of finished MWCNTs powder (with the particle size of 30 mu m) and 110g of finished graphite powder (with the particle size of 30 mu m) into a kneader for mixing, pouring 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water, kneading, extruding, rolling ball forming, and drying at 100 ℃ for 12 hours to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of H containing 2gPt2PtCl6The methanol solutions were mixed and impregnated. Standing at room temperature for 6h, then drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 420 ℃ for 3.0h to obtain the catalyst precursor. 450 ℃ in H2-N2Reducing for 3.5H in the atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ example 5 ]
1. Preparation of the support
Mixing 132g of finished MWCNTs powder (with the particle size of 30 mu m) and 88g of finished graphite powder (with the particle size of 30 mu m) in a kneader, pouring 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water, kneading, extruding, rolling ball forming, and drying at 100 ℃ for 12 hours to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of H containing 2gPt2PtCl6The methanol solutions were mixed and impregnated. Standing at room temperature for 6h, then drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 420 ℃ for 3.0h to obtain the catalyst precursor. 450 ℃ in H2-N2Reducing for 3.5H in the atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ example 6 ]
1. Preparation of the support
88g of finished MWCNTs powder (with the particle size of 30 mu m) and 132g of finished graphite powder (with the particle size of 30 mu m) are put into a kneader to be mixed, 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water are poured, kneading, extruding, rolling ball forming are carried out, and drying is carried out at 100 ℃ for 12 hours, so as to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of H containing 2gPt2PtCl6The methanol solutions were mixed and impregnated. Standing at room temperature for 6h, then drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 420 ℃ for 3.0h to obtain the catalyst precursor. 450 ℃ in H2-N2Reducing for 3.5H in the atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ example 7 ]
1. Preparation of the support
And (2) putting 110g of finished MWCNTs powder (with the particle size of 30 mu m) and 110g of finished graphite powder (with the particle size of 30 mu m) into a kneader for mixing, pouring 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water, kneading, extruding, rolling ball forming, and drying at 100 ℃ for 12 hours to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of PdCl containing 2gPd2The methanol solutions were mixed and impregnated. Standing at room temperature for 6h, drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 480 ℃ for 2.5h to obtain the catalyst precursor. At 350 ℃ in H2-N2Reducing for 4.5H in the atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ example 8 ]
1. Preparation of the support
Mixing 132g of finished MWCNTs powder (with the particle size of 30 mu m) and 88g of finished graphite powder (with the particle size of 30 mu m) in a kneader, pouring 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water, kneading, extruding, rolling ball forming, and drying at 100 ℃ for 12 hours to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of PdCl containing 2gPd2The methanol solutions were mixed and impregnated. Standing at room temperature for 6h, drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 480 ℃ for 2.5h to obtain the catalyst precursor. At 350 ℃ in H2-N2Reducing for 4.5H in the atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. COD removal was calculated at 24 hours of evaluationAnd (4) rate.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ example 9 ]
1. Preparation of the support
88g of finished MWCNTs powder (with the particle size of 30 mu m) and 132g of finished graphite powder (with the particle size of 30 mu m) are put into a kneader to be mixed, 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water are poured, kneading, extruding, rolling ball forming are carried out, and drying is carried out at 100 ℃ for 12 hours, so as to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of PdCl containing 2gPd2The methanol solutions were mixed and impregnated. Standing at room temperature for 6h, drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 480 ℃ for 2.5h to obtain the catalyst precursor. At 350 ℃ in H2-N2Reducing for 4.5H in the atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ COMPARATIVE EXAMPLE 1 ]
1. Preparation of the support
220g MWCNTs powder (with the particle size of 30 mu m) is put into a kneader, 20g PEG400 aqueous solution with the concentration of 15 wt% and 50g water are poured, kneading, extruding, rolling ball forming are carried out, and drying is carried out at 100 ℃ for 12h, so that the spherical carrier with the diameter of 3mm is obtained.
2. Catalyst preparation
198g of spherical carrier and 300g of RuCl containing 2gRu3The methanol solution was mixed. Standing at room temperature for 6h, drying in an oven at 110 deg.C for 16h, and then drying in a horse furRoasting the mixture for 2.5 hours at the temperature of 450 ℃ in a furnace to obtain a catalyst precursor. At 400 ℃ in H2-N2Reducing for 4.0H in atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ COMPARATIVE EXAMPLE 2 ]
1. Preparation of the support
Putting 220g of graphite powder (with the particle size of 30 mu m) into a kneader, pouring 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water, kneading, extruding, rolling ball forming, and drying at 100 ℃ for 12h to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of RuCl containing 2gRu3The methanol solution was mixed. Standing at room temperature for 6h, then drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 450 ℃ for 2.5h to obtain the catalyst precursor. At 400 ℃ in H2-N2Reducing for 4.0H in atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ COMPARATIVE EXAMPLE 3 ]
1. Preparation of the support
220g MWCNTs powder (with the particle size of 30 mu m) is put into a kneader, 20g PEG400 aqueous solution with the concentration of 15 wt% and 50g water are poured, kneading, extruding, rolling ball forming are carried out, and drying is carried out at 100 ℃ for 12h, so that the spherical carrier with the diameter of 3mm is obtained.
2. Catalyst preparation
198g of spherical carrier and 300g of H containing 2gPt2PtCl6The methanol solution was mixed. Standing at room temperature for 6h, then drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 420 ℃ for 3.0h to obtain the catalyst precursor. 450 ℃ in H2-N2Reducing for 3.5H in the atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ COMPARATIVE EXAMPLE 4 ]
1. Preparation of the support
Putting 220g of graphite powder (with the particle size of 30 mu m) into a kneader, pouring 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water, kneading, extruding, rolling ball forming, and drying at 100 ℃ for 12h to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of H containing 2gPt2PtCl6The methanol solution was mixed. Standing at room temperature for 6h, then drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 420 ℃ for 3.0h to obtain the catalyst precursor. Reducing at 450 ℃ for 3.5H in an atmosphere of H2-N2 to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of catalyst was taken and charged in a wet containerThe oxidation reactor is used for reaction. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ COMPARATIVE EXAMPLE 5 ]
1. Preparation of the support
220g MWCNTs powder (with the particle size of 30 mu m) is put into a kneader, 20g PEG400 aqueous solution with the concentration of 15 wt% and 50g water are poured, kneading, extruding, rolling ball forming are carried out, and drying is carried out at 100 ℃ for 12h, so that the spherical carrier with the diameter of 3mm is obtained.
2. Catalyst preparation
198g of spherical carrier and 300g of PdCl containing 2gPd2The methanol solution was mixed. Standing at room temperature for 6h, drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 480 ℃ for 2.5h to obtain the catalyst precursor. At 350 ℃ in H2-N2Reducing for 4.5H in the atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
[ COMPARATIVE EXAMPLE 6 ]
1. Preparation of the support
Putting 220g of graphite powder (with the particle size of 30 mu m) into a kneader, pouring 20g of PEG400 aqueous solution with the concentration of 15 wt% and 50g of water, kneading, extruding, rolling ball forming, and drying at 100 ℃ for 12h to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
198g of spherical carrier and 300g of PdCl containing 2gPd2The methanol solution was mixed. Standing at room temperature for 6h, drying in an oven at 110 ℃ for 16h, and then roasting in a muffle furnace at 480 ℃ for 2.5h to obtain the catalyst precursor. At 350 ℃ in H2-N2Reducing for 4.5H in the atmosphere to obtain the catalyst, wherein H2:N2The volume ratio was 4: 96.
3. Catalyst evaluation
100g of the catalyst was charged into a wet oxidation reactor and reacted. The reaction temperature is 280 ℃, the pressure is 9.0MPa, the volume ratio of oxygen to industrial wastewater is 200, and the mass space velocity of the industrial wastewater is 1.0h-1. The reaction product was subjected to COD analysis by a Hach COD analyzer to determine the COD value. The removal rate of COD was calculated at the evaluation time of 24 hours.
The composition of the support, the composition of the catalyst and the evaluation results of the catalyst are shown in Table 1, and the main preparation conditions of the catalyst are shown in Table 2.
TABLE 1
Figure BDA0000963764490000121
TABLE 2 catalyst preparation Process
Figure BDA0000963764490000131

Claims (10)

1. The heterogeneous catalysis wet oxidation catalyst comprises the following components in parts by weight:
a)98.0 ~ 99.8.8 parts of carrier, and carrier supported thereon
b)0.2 ~ 2.0.0 part of at least one of Ru, Pd, Pt and Rh;
the support comprises a composite of multi-walled carbon nanotubes and graphite.
2. The catalyst of claim 1, wherein the mass ratio of multi-walled carbon nanotubes to graphite in the composite is 1:4 ~ 4: 1.
3. A process for preparing a catalyst as claimed in claim 1 or 2, comprising the steps of:
1) mixing the required carrier powder and a binder, extruding and molding, and drying;
2) loading the solution I on a carrier by adopting an impregnation method, drying, and roasting at 350 ~ 600 ℃ for 1.5 ~ 5.0.0 h to prepare a catalyst precursor;
3) reducing the catalyst precursor with hydrogen at 300 ~ 500 ℃ for 2.5 ~ 5h to obtain the catalyst;
the solution I is prepared by at least one salt selected from Ru, Pd, Pt and Rh and an organic solvent.
4. The method according to claim 3, wherein the calcination temperature in the step 2) is 400 ~ 550 ℃.
5. The method according to claim 3, wherein the reduction temperature in the step 3) is 350 ~ 450 ℃.
6. A method for treating waste water generated in the production of acrylonitrile by ammoxidation of propylene or propane, which comprises mixing industrial waste water generated in the production of acrylonitrile with oxygen and reacting the mixture in a wet oxidation reactor containing the catalyst of claim 1 or 2.
7. The process according to claim 6, wherein the reaction temperature is 220 to 300 ℃.
8. The process according to claim 6, wherein the reaction pressure is 5.0 to 10.0 MPa.
9. The treatment method according to claim 6, wherein the volume ratio of the oxygen to the industrial wastewater is 50 to 400.
10. The treatment method according to claim 6, wherein the mass space velocity of the industrial wastewater is 0.5-1.5h-1。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN104043452A (en) * 2013-03-13 2014-09-17 中国石油化工股份有限公司 Heterogeneous catalytic wet oxidation catalyst using active carbon as carrier and preparation method thereof
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CN104043452A (en) * 2013-03-13 2014-09-17 中国石油化工股份有限公司 Heterogeneous catalytic wet oxidation catalyst using active carbon as carrier and preparation method thereof
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