CN111072125A - Treatment method of aldehyde-containing wastewater - Google Patents

Treatment method of aldehyde-containing wastewater Download PDF

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Publication number
CN111072125A
CN111072125A CN201811214328.8A CN201811214328A CN111072125A CN 111072125 A CN111072125 A CN 111072125A CN 201811214328 A CN201811214328 A CN 201811214328A CN 111072125 A CN111072125 A CN 111072125A
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parts
catalyst
wastewater
reaction
metal oxide
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陈航宁
郑育元
许丹丹
郭宗英
吴粮华
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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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    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen

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

Abstract

The invention relates to a treatment method of aldehyde-containing wastewater, which is used for solving the problem of low efficiency of reducing aldehyde in wastewater by the existing method and comprises the steps of carrying out oxidation reaction on the aldehyde-containing wastewater and hydrogen peroxide under the acidic condition and under the catalysis of a catalyst; wherein the catalyst comprises a carrier and an active component comprising a metal selected from the group consisting of CeO2、Fe2O3、CuO、MnO2And at least one of the substance groups consisting of noble metals, thereby better solving the problem and being used for treating the aldehyde-containing wastewater.

Description

Treatment method of aldehyde-containing wastewater
Technical Field
The invention relates to a method for treating aldehyde-containing wastewater.
Technical Field
Formaldehyde is high in toxicity, is the second place on the toxic chemical list in China, is determined as a teratogenic and mutagenic substance by the world health organization and the United states environmental protection agency, and is determined as a carcinogenic substance by the world cancer society. Because it can cause large-area death of biological strains, if the water contains high-concentration formaldehyde, the biochemical difficulty is extremely high.
The multiphase Fenton oxidation method is particularly suitable for treating medium-low concentration wastewaterAldehyde wastewater. The method is to decompose hydrogen peroxide to generate hydroxyl free radicals with strong oxidizing property in the presence of a catalyst, and finally oxidize organic pollutants in the wastewater into CO2And inorganic substances such as water and the like or micromolecular organic substances, and the process is a green, energy-saving and environment-friendly organic wastewater treatment method. The Fenton process is a commonly used catalytic wet hydrogen peroxide process in which Fe is used2+/H2O2In the presence of the catalyst, the aldehyde-containing compound is oxidized into organic acid which is easy to be biodegraded or deeply oxidized into carbon dioxide and water. However, the method has the disadvantages that the pH value is strictly controlled in the reaction process, iron ions need to be removed after the reaction, and the operation is complicated. The heterogeneous catalyst has the advantages of easy separation, repeated use and the like, and greatly increases the industrial application value of the technology, so that the development of an efficient and stable wet hydrogen peroxide catalyst is the key point of the research field in recent years.
The invention discloses an organic wastewater treatment process, which comprises the following steps: materialization pretreatment, anaerobic hydrolysis acidification treatment and TCBS system treatment. The invention can improve the biodegradability of organic wastewater, enhance the toxicity resistance and impact resistance of a system, strengthen the biological denitrification function of the system, and enable the organic wastewater to meet the national environmental protection requirements by reducing pollution load step by step. But the method is only suitable for treating the low-concentration formaldehyde wastewater.
CN101553436 discloses an apparatus for treating high concentration organic wastewater and a method for treating organic wastewater using the same. An apparatus for treating high concentration organic wastewater includes a carrier reactor that receives organic wastewater to be treated and oxidatively decomposes organic materials included in the organic wastewater using aerobic microorganisms attached to carriers. However, this method is not suitable for treating organic waste water containing biological toxicity.
CN1030983 discloses a method for treating phenolic aldehyde-containing wastewater by using a photocatalytic method. In the invention, in phenolic aldehyde-containing wastewater, 10-15 ml of concentrated HCl per liter is polymerized for 5 hours at the temperature of 80-90 ℃, phenolic resin is recovered, and then TiO is added into the phenolic resin-removed wastewater2，MnO2Heating the catalyst to 60 deg.C, stirring, introducing air, and irradiating under lightDegrading to make phenol reach 0.5-1 mg/liter discharge, but the photocatalysis treatment efficiency is low.
Disclosure of Invention
The invention aims to solve the technical problem of low formaldehyde removal efficiency in the treatment of aldehyde-containing wastewater in the prior art, and provides a novel treatment method of aldehyde-containing wastewater, which has the advantage of high formaldehyde removal efficiency.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the treatment method of aldehyde-containing wastewater comprises the steps of carrying out oxidation reaction on the aldehyde-containing wastewater and hydrogen peroxide under the acidic condition and the catalysis of a catalyst; wherein the catalyst comprises a carrier and an active component comprising a metal selected from the group consisting of CeO2、Fe2O3、CuO、MnO2And a noble metal.
The active component can effectively reduce the content of formaldehyde in the wastewater.
The technical key of the invention is the selection of the catalyst, and after the catalyst is determined, the specific process conditions of the oxidation treatment can be reasonably determined by a person skilled in the art without creative labor.
In the above technical scheme, the reactor used in the reaction may be one selected from a fixed bed, a fluidized bed or a reaction kettle.
In the above technical scheme, the reaction time may be 10 to 120 minutes, and further 20 to 110 minutes.
In the technical scheme, the using amount of the hydrogen peroxide can be 1-10 times of that of the stoichiometric hydrogen peroxide needed by the formaldehyde in the wastewater.
In the above-mentioned embodiment, the acidifying agent used to satisfy the acidic condition required for the reaction may include at least one selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid.
In the above technical solution, the pH value of the acidic condition may be more than 1 and less than 7.
In the technical scheme, the temperature of the oxidation reaction can be 0-80 ℃.
Technical matters of the inventionThe bond is the choice of active ingredient, and the person skilled in the art can make a rational choice of the carrier used without having to resort to inventive work and all with comparable technical results. For example, but not limited to, the support comprises a material selected from the group consisting of TiO2、ZrO2、Al2O3、SiO2And activated carbon.
In the above technical solution, the noble metal includes at least one selected from a group consisting of Ru, Au, and Pt, and the noble metal preferably includes Au.
In the above technical solution, the active component preferably includes Au and the metal oxide at the same time, and Au and the metal oxide have a synergistic effect in removing formaldehyde in the aldehyde-containing wastewater by fenton oxidation. The ratio of Au to the metal oxide is not particularly limited as long as both are present at the same time to achieve a comparable synergistic effect. By way of a limiting example, the catalyst comprises in parts by weight:
(1) more than 0 part and less than 40 parts of metal oxide;
(2) more than 0 part and less than 10 parts of Au;
(3) a carrier in an amount greater than 50 parts and less than 100 parts;
wherein the metal oxide comprises a metal selected from the group consisting of CeO2、Fe2O3CuO and MnO2At least one of the group of substances.
In the above technical solution, the metal oxide preferably includes both a first metal oxide and a second metal oxide, and the first metal oxide includes Fe2O3CuO and MnO2At least one of the group of substances, the second metal oxide being CeO2The first metal oxide and the second metal oxide have a synergistic effect in removing formaldehyde in the aldehyde-containing wastewater by fenton oxidation. The ratio of the first metal oxide to the second metal oxide is not particularly limited as long as both are present to achieve a comparable synergistic effect. As a limiting example, the mass ratio of the first metal oxide to the second metal oxide may be 0.1 to 10, within this mass ratio range, notLimiting specific mass ratio values may be, for example, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9.0, and the like.
In the above technical solution, it is more preferable that the metal oxide composition further includes Au, a first metal oxide and a second metal oxide, and the three have a synergistic effect in removing formaldehyde in the aldehyde-containing wastewater by fenton oxidation.
In the above technical scheme, the catalyst can be obtained by a preparation method comprising the step of loading an active component on a carrier.
When the catalyst "comprises the following components in parts by weight:
(1) more than 0 part and less than 40 parts of metal oxide;
(2) more than 0 part and less than 10 parts of Au;
(3) a carrier in an amount greater than 50 parts and less than 100 parts;
wherein the metal oxide comprises a metal selected from the group consisting of CeO2、Fe2O3CuO and MnO2In the case of at least one member of the group consisting of, the method for preparing the catalyst preferably comprises the steps of:
(1) mixing a compound containing metal elements in the metal oxide with a carrier, extruding and molding, and roasting to obtain a precursor A;
(2) preparing a solution from an Au compound, mixing the solution with the precursor A, drying and roasting to obtain the catalyst.
In the above technical scheme, the compound of Fe, Mn, Cu, Ce is preferably selected from one of acetate, nitrate or chloride.
In the technical scheme, the roasting temperature in the step (1) is preferably 200-600 ℃, and the roasting time is preferably 1-12 h.
In the technical scheme, the roasting temperature in the step (2) is preferably 300-500 ℃, and the roasting time is preferably 1-12 h.
To solve the third technical problem, the technical scheme of the invention is as follows:
the treatment method of aldehyde-containing wastewater comprises the step of carrying out oxidation reaction on the aldehyde-containing wastewater and hydrogen peroxide under the acidic condition and under the catalysis of the catalyst in any one of the technical schemes in one of the technical problems.
The technical key of the invention is the selection of the catalyst, and after the composition of the catalyst is determined, a person skilled in the art can reasonably select the specific process conditions of the oxidation reaction without creative labor and can obtain comparable technical effects. By way of non-limiting example, for example:
in the above technical scheme, the reactor used in the reaction can be selected from one of a fixed bed, a fluidized bed or a reaction kettle.
In the technical scheme, the reaction time can be 10-120 minutes.
In the technical scheme, the using amount of the hydrogen peroxide can be 1-10 times of that of stoichiometric hydrogen peroxide needed by formaldehyde in the wastewater.
In the above technical scheme, the acidifying agent used to satisfy the acidic conditions required for the reaction includes at least one selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid.
In the above technical solution, the pH value of the acidic condition may be more than 1 and less than 7.
In the above technical scheme, the temperature of the oxidation reaction can be 0-80 ℃, and further 20-60 ℃.
In the above technical scheme, the formaldehyde content in the aldehyde-containing wastewater can be more than 0mg/L and less than 3,000mg/L, such as but not limited to 100mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 800mg/L, 1000mg/L, 1200mg/L, 1500mg/L, 1600mg/L, 1800mg/L, 2000mg/L, 2200mg/L, 2400mg/L, 2600mg/L, 2800mg/L, and the like.
By adopting the technical scheme, the result shows that the catalyst prepared by the method can effectively reduce the organic content of the aldehyde-containing wastewater under the conditions of 50 ℃ of reaction temperature, 0.2MPa of pressure and 60 minutes of retention time, and the residual formaldehyde content is less than 12mg/L after Fenton oxidation treatment, so that 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. Catalyst preparation
The preparation method of the metal oxide comprises the following steps:
(1) will contain equivalent to 6 parts of CeO2Ce (NO) of3)350 parts of aqueous solution, then adding 10 parts of citric acid and 6 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
mixing 54 parts of activated carbon, 6 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 2 ]
1. Catalyst preparation
The preparation method of the metal oxide comprises the following steps:
(1) will contain an amount of Fe equivalent to 6 parts2O3Fe (NO) of3)350 parts of aqueous solution, then adding 10 parts of citric acid and 6 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
mixing 54 parts of activated carbon, 6 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 3 ]
1. Catalyst preparation
The preparation method of the metal oxide comprises the following steps:
(1) cu (NO) corresponding to 6 parts of CuO3)250 parts of aqueous solution, then adding 10 parts of citric acid and 6 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
mixing 54 parts of activated carbon, 6 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 4 ]
1. Catalyst preparation
The preparation method of the metal oxide comprises the following steps:
(1) will contain an amount equivalent to 6 parts of MnO2Mn (NO) of3)250 parts of water solution, 10 parts of citric acid and 6 parts of glycol are added into the mixture, and the mixture is added into sandEvaporating to dryness in bath to obtain precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
mixing 54 parts of activated carbon, 6 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 5 ]
1. Catalyst preparation
And (3) forming of the catalyst:
(1) mixing 54 parts of activated carbon, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst precursor.
(2) 94 parts of catalyst precursor were impregnated with HAuCl containing 6 parts of Au420 parts of the aqueous solution was dried at 80 ℃ for 12 hours, and then calcined at 400 ℃ for 4 hours in an air atmosphere to obtain a catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 6 ]
1. Catalyst preparation
The preparation method of the composite metal oxide comprises the following steps:
(1) will contain equivalent to 3 parts of Fe2O3And 3 parts of CeO2Fe (NO) of3)3-Ce(NO3)350 parts of aqueous solution, then adding 10 parts of citric acid and 6 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
mixing 54 parts of activated carbon, 6 parts of composite metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 7 ]
1. Catalyst preparation
The preparation method of the composite metal oxide comprises the following steps:
(1) will contain equivalent to 3 parts of CuO and 3 parts of CeO2Cu (NO) of3)2-Ce(NO3)350 parts of aqueous solution, then adding 10 parts of citric acid and 6 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the composite metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
mixing 54 parts of activated carbon, 6 parts of composite metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 8 ]
1. Catalyst preparation
The preparation method of the composite metal oxide comprises the following steps:
(1) will contain an amount equivalent to 3 parts of MnO2And 3 parts of CeO2Ce (NO) of3)3-Mn(NO3)250 parts of aqueous solution, then adding 10 parts of citric acid and 6 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the composite metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
mixing 54 parts of activated carbon, 6 parts of composite metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 9 ]
1. Catalyst preparation
The preparation method of the metal oxide comprises the following steps:
(1) ce (NO) corresponding to 3 parts of CeO3)350 parts of aqueous solution is addedDrying 10 parts of citric acid and 6 parts of ethylene glycol in a sand bath to dryness to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
(1) mixing 54 parts of activated carbon, 3 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst precursor.
(2) 97 parts of catalyst precursor were impregnated with 3 parts of Au-containing HAuCl420 parts of the aqueous solution was dried at 80 ℃ for 12 hours, and then calcined at 400 ℃ for 4 hours in an air atmosphere to obtain a catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 10 ]
1. Catalyst preparation
The preparation method of the metal oxide comprises the following steps:
(1) will contain equivalent to 3 parts of Fe2O3Fe (NO) of3)3Adding 25 parts of aqueous solution into 5 parts of citric acid and 3 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
(1) mixing 54 parts of activated carbon, 3 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst precursor.
(2) 97 parts of catalyst precursor were impregnated with 3 parts of Au-containing HAuCl420 parts of the aqueous solution are dissolved at 80 DEG CDried for 12 hours and then calcined at 400 ℃ for 4 hours in an air atmosphere to obtain the catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 11 ]
1. Catalyst preparation
The preparation method of the metal oxide comprises the following steps:
(1) cu (NO) corresponding to 3 parts of CuO3)2Adding 25 parts of aqueous solution into 5 parts of citric acid and 3 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
(1) mixing 54 parts of activated carbon, 3 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst precursor.
(2) 97 parts of catalyst precursor were impregnated with 3 parts of Au-containing HAuCl420 parts of the aqueous solution was dried at 80 ℃ for 12 hours, and then calcined at 400 ℃ for 4 hours in an air atmosphere to obtain a catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 12 ]
1. Catalyst preparation
The preparation method of the metal oxide comprises the following steps:
(1) will contain an amount equivalent to 3 parts of MnO2Mn (NO) of3)2Adding 25 parts of aqueous solution into 5 parts of citric acid and 3 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
(1) mixing 54 parts of activated carbon, 3 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst precursor.
(2) 97 parts of catalyst precursor were impregnated with 3 parts of Au-containing HAuCl420 parts of the aqueous solution was dried at 80 ℃ for 12 hours, and then calcined at 400 ℃ for 4 hours in an air atmosphere to obtain a catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 13 ]
1. Catalyst preparation
The preparation method of the composite metal oxide comprises the following steps:
(1) will contain 2 parts of Fe2O3And 2 parts of CeO2Fe (NO) of3)3-Ce(NO3)3Adding 35 parts of aqueous solution into 7.5 parts of citric acid and 4 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
(1) mixing 54 parts of activated carbon, 4 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst precursor.
(2) 98 parts of catalyst precursor were impregnated with 2 parts of Au-containing HAuCl420 parts of the aqueous solution was dried at 80 ℃ for 12 hours, and then calcined at 400 ℃ for 4 hours in an air atmosphere to obtain a catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 14 ]
1. Catalyst preparation
The preparation method of the composite metal oxide comprises the following steps:
(1) will contain equivalent to 2 parts of CuO and 2 parts of CeO2Cu (NO) of3)2-Ce(NO3)3Adding 35 parts of aqueous solution into 7.5 parts of citric acid and 4 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the composite metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
(1) mixing 54 parts of activated carbon, 4 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst precursor.
(2) 98 parts of catalyst precursor were impregnated with 2 parts of Au-containing HAuCl420 parts of the aqueous solution was dried at 80 ℃ for 12 hours, and then calcined at 400 ℃ for 4 hours in an air atmosphere to obtain a catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
[ example 15 ]
1. Catalyst preparation
The preparation method of the composite metal oxide comprises the following steps:
(1) will contain an amount equivalent to 2 parts of MnO2And 2 parts of CeO2Ce (NO) of3)3-Mn(NO3)2Adding 35 parts of aqueous solution into 7.5 parts of citric acid and 4 parts of glycol, and evaporating to dryness in a sand bath to obtain a precursor;
(2) and roasting the precursor at 600 ℃ for 4h to obtain the composite metal oxide, and pulverizing for later use.
And (3) forming of the catalyst:
(1) mixing 54 parts of activated carbon, 4 parts of metal oxide, 40 parts of alumina and 5 parts of water, tabletting, forming, drying, and roasting at 400 ℃ for 4 hours to obtain the catalyst precursor.
(2) 98 parts of catalyst precursor were impregnated with 2 parts of Au-containing HAuCl420 parts of the aqueous solution was dried at 80 ℃ for 12 hours, and then calcined at 400 ℃ for 4 hours in an air atmosphere to obtain a catalyst. The catalyst formulation is shown in table 1.
2. Catalyst evaluation
Industrial acrylic acid wastewater is used as a raw material, and the content of formaldehyde in the wastewater is 2186 mg/L. The pH was adjusted to 3.5 with sulfuric acid before the reaction. The wastewater was mixed with hydrogen peroxide and passed through a 120mL fixed bed reactor packed with 85g of catalyst. The amount of the hydrogen peroxide is 5.5 times of the amount calculated by the formaldehyde in the industrial acrylic acid wastewater. The reaction temperature in the reactor was 40 ℃, the pressure 0.2MPa, and the residence time 90 minutes. The reaction results are shown in Table 2.
TABLE 1 formulation of the catalyst
Figure BDA0001833166550000131
TABLE 2 reaction results
Figure BDA0001833166550000141

Claims (10)

1. The treatment method of aldehyde-containing wastewater comprises the steps of carrying out oxidation reaction on the aldehyde-containing wastewater and hydrogen peroxide under the acidic condition and the catalysis of a catalyst; wherein the catalyst comprises a carrier and an active component comprising a metal selected from the group consisting of CeO2、Fe2O3、CuO、MnO2And a noble metal.
2. The process as set forth in claim 1, wherein the reactor used in the reaction is selected from the group consisting of a fixed bed, a fluidized bed and a reaction vessel.
3. The method according to claim 1, wherein the reaction time is 10 to 120 minutes.
4. The process according to claim 3, wherein the reaction time is 20 to 110 minutes.
5. The method as set forth in claim 1, wherein the amount of the hydrogen peroxide is 1 to 10 times the stoichiometric amount of the hydrogen peroxide required for the formaldehyde in the wastewater.
6. The process as set forth in claim 1, characterized in that the acidifying agent used for satisfying the acidic condition required for the reaction comprises at least one member selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid.
7. The process according to claim 1, characterized in that the pH value of the acidic conditions is greater than 1 and lower than 7.
8. The method according to claim 1, wherein the temperature of the oxidation reaction is 0 to 80 ℃.
9. The process of claim 1, wherein the support comprises a material selected from the group consisting of TiO2、ZrO2、Al2O3、SiO2And activated carbon.
10. The process as set forth in claim 1, characterized in that the catalyst is obtained by a preparation method comprising a step of supporting an active component on a carrier.
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