CN109574188A - The wet oxidation processing method of formaldehyde-containing wastewater - Google Patents

The wet oxidation processing method of formaldehyde-containing wastewater Download PDF

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Publication number
CN109574188A
CN109574188A CN201710895371.4A CN201710895371A CN109574188A CN 109574188 A CN109574188 A CN 109574188A CN 201710895371 A CN201710895371 A CN 201710895371A CN 109574188 A CN109574188 A CN 109574188A
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catalyst
wet oxidation
formaldehyde
processing method
parts
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CN109574188B (en
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陈航宁
郭宗英
郑育元
许丹丹
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
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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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Abstract

The present invention relates to the wet oxidation processing methods of formaldehyde-containing wastewater.To solve the problems, such as to reduce aldehyde low efficiency in waste water in existing method.The present invention passes through the wet oxidation processing method of formaldehyde-containing wastewater, it is included in the presence of wet oxidation heterogeneous catalyst, the waste water and oxygenous oxidant are reacted to the formaldehyde removed in waste water in the reactor, the wet oxidation heterogeneous catalyst, in parts by weight, including following components: (1) 90~99.5 parts of catalyst carrier；(2) 0.1~5 parts of technical solutions selected from least one of platinum family noble metal, preferably solve the problems, such as this, the high-concentration formaldehyde that can be used in fast degradation waste water.

Description

The wet oxidation processing method of formaldehyde-containing wastewater
Technical field
The present invention relates to the wet oxidation processing methods of formaldehyde-containing wastewater, more particularly to the wet type oxygen of industrial acrylic acid wastewater Change processing method.
Technical background
Formaldehyde toxicity is big, occupies second on China's toxic chemical list, is protected by the World Health Organization and U.S. environment Shield office is determined as teratogenesis, mutagenic matter, is determined as carcinogen by cancer association, the world.Because it can lead to the big of biological inoculum Area is dead, if containing high-concentration formaldehyde in water, biochemical difficulty is very big.Catalytic wet oxidation is that a kind of processing middle and high concentration is organic The platform technology of waste water.Its main feature is that organic wastewater is under the conditions of high temperature (125~320 DEG C), high pressure (0.5~20MPa), with sky Gas or pure oxygen are that organic pollutant is oxidized to CO in liquid phase under the effect of the catalyst by oxidant2With inorganic matters such as water or small Molecular organic.The technique is a kind of method for processing organic wastewater of energy-saving and environment friendly, is highly suitable for high concentration organic waste The processing of water.
CN1631818 disclosure of the invention a kind of organic wastewater treatment process, step include: materialized pretreatment, anaerobism water Solve acidification and the processing of TCBS system.The invention can be improved organic wastewater biodegradability, enhancing system resistance to poison with it is resistance to Impact, consolidation system biological denitrificaion function reach national requirements for environmental protection by cut down that pollutional load makes organic wastewater step by step. But this method is only applicable to processing low concentration formaldehyde waste water.
CN101553436, which is disclosed a kind of device for handling high concentrated organic wastewater and handled using the device, to be had The method of machine waste water.Device for handling high concentrated organic wastewater includes carrier reactor, which receives wait locate The organic wastewater of reason, and include organic material in organic wastewater come oxygenolysis using the aerobe for being attached to carrier Material.But this method is not suitable for handling the organic wastewater containing bio-toxicity.
CN1030983 discloses a kind of method using treating phenolic aldehyde bearing waste water by photocatalysis.The invention is containing phenolic aldehyde In waste water, by the dense HCl of every liter of 10~15ml, temperature control polymerize 5 hours at 80~90 DEG C, recycles phenolic resin, then will remove phenol TiO is added in the waste water of urea formaldehyde2, MnO2Catalyst is heated to 60 DEG C, and stirring, blowing air degrades under illumination, phenol is made to reach 0.5 ~1mg/ is discharged when rising, but photocatalytic method treatment effeciency is low.
Summary of the invention
The technical problem to be solved by the present invention is to the low efficiencys of wet oxidizing catalyst in the prior art removing COD Problem provides a kind of wet oxidation processing method of new high concentrated organic wastewater, and this method, which has, removes the high-efficient of COD Advantage.
In order to solve the above technical problems, technical scheme is as follows:
The wet oxidation processing method of formaldehyde-containing wastewater, is included in the presence of wet oxidation heterogeneous catalyst, will be described Waste water and oxygenous oxidant react in the reactor remove waste water in formaldehyde, the wet oxidation heterogeneous catalyst, with Parts by weight meter, including following components:
(1) 90~99.5 part of catalyst carrier；
(2) 0.1~5 parts selected from least one of platinum family noble metal.
In above-mentioned technical proposal, the oxidant is preferably air or oxygen.
In above-mentioned technical proposal, the temperature of reaction is preferably 120~200 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 2~5MPa.
In above-mentioned technical proposal, the residence time of waste water is preferably 5~60 minutes.
In above-mentioned technical proposal, the catalyst carrier preferably is selected from TiO2、ZrO2、SiO2And Al2O3One of.
In above-mentioned technical proposal, the noble metal preferably is selected from least one of Ru, Pd, Pt, Ir and Rh.
In above-mentioned technical proposal, the catalyst has comparable effect to any concentration organic wastewater, but to high concentration The processing of organic wastewater more has apparent advantage.The COD value of the formaldehyde-containing wastewater is preferably 10,000~200,000mg/L.
In above-mentioned technical proposal, it is also preferable to include (3) 0.1~5 parts of co-catalysts, the co-catalyst choosings for the catalyst From at least one of copper and tin.Noble metal has both in terms of the effect of removing formaldehyde with co-catalyst significantly cooperates with effect It answers.
In above-mentioned technical proposal, the co-catalyst more preferably includes copper and tin simultaneously, and copper and tin is in removing organic wastewater In formaldehyde effect in terms of both have apparent synergistic effect.At this point, the weight ratio of copper and tin is not particularly limited, such as But being not limited to copper and tin is 0.1~10, and in this ratio range, more specific unrestricted weight ratio point value be can be 0.21、0.41、0.61、0.81、1.01、1.51、2.01、2.51、3.01、3.51、4.01、4.51、5.01、5.51、6.1、8.1 Etc..
In above-mentioned technology, the wet oxidation heterogeneous catalyst can be using the preparation method preparation included the following steps:
1) compound solution containing precious metal element is mixed with carrier；
2) the compound state noble metal for introducing step 1) is simple substance.
In above-mentioned technical proposal, when containing cocatalyst in the catalyst, the preparation method may further be The method one included the following steps:
(1) mixed aqueous solution of the compound containing noble metal and compound and containing co-catalyst is mixed with carrier；
(2) noble metal of compound state and co-catalyst are reduced to simple substance.
In above-mentioned technical proposal, when containing cocatalyst in the catalyst, the preparation method may further For the method two included the following steps:
1) solution of the compound containing precious metal element is mixed with carrier；
2) roasting obtains catalyst precarsor I；
3) compound solution containing promoter elements is mixed with precursor I；
4) the compound state metal of introducing is reduced to simple substance.
In above-mentioned technical proposal, when containing cocatalyst in the catalyst, the preparation method may further For the method three included the following steps:
(i) compound water solution containing co-catalyst is mixed with carrier, dry, roasting obtains catalyst precursor I；
(ii) aqueous solution containing precious metal chemical complex is mixed with catalyst precursor I；
(iii) the compound state noble metal for introducing step (ii) is simple substance.
Three kinds of methods are compared, and when the catalyst prepared using method three, the present invention has unusual in terms of removing formaldehyde Good technical effect.
In above-mentioned technical proposal, the specific method of reduction is not particularly limited, as long as can be the active component of compound state also It originally is simple substance.For example, vapour phase reduction can be carried out to predecessor with gaseous reducing agent, the solution of reducing agent can also be used Or liquid-phase reduction agent carries out liquid-phase reduction.Gaseous reducing agent commonly may include the gas of hydrogen, such as hydrogen, hydrogen-nitrogen Gas gaseous mixture etc..The reducing agent of liquid-phase reduction can be hydrazine hydrate, formic acid or sodium formate etc..
In above-mentioned technical proposal, the compound containing tin element preferably is selected from tin oxalate, appointing in tin tetrachloride and stannous chloride It anticipates one kind.
In above-mentioned technical proposal, the compound containing copper preferably is selected from copper nitrate, copper chloride, copper sulphate and copper acetate Any one.
In above-mentioned technical proposal, the compound of the noble metal active component is not particularly limited, and such as, but not limited to three Ruthenic chloride, palladium chloride, chlorine palladium acid, chloroplatinic acid, radium chloride etc..
In above-mentioned technical proposal, catalyst precursor I roasting process carries out in air atmosphere, and the temperature of roasting is preferred 300~600 DEG C, the time of roasting is preferably 2~4.5 hours.
One skilled in the art will appreciate that when hydrogen is that reducing agent is restored, it is for safety preferred with volume basis Hydrogen content is 5% hydrogen nitrogen mixture below.
In above-mentioned technical proposal, when being restored using hydrogen, reduction temperature is preferably 300~700 DEG C, further preferably 350~600 DEG C；Recovery time is preferably 1~5 hour, and further preferred 2.5~4.5 hours.
Key problem in technology of the invention is the selection of catalyst, and the source of formaldehyde-containing wastewater is not particularly limited, such as but It is not limited to industrial acrylic acid wastewater.
Using technical solution of the present invention, the results showed that be catalyzed with the C-10 of prepared by the present invention while platiniferous, tin and copper Agent is 180 DEG C, pressure 4MPa in reaction temperature, and the residence time is that can effectively reduce the height in waste water under conditions of 30 minutes Concentration formaldehyde, after wet oxidation is handled, the removal rate of formaldehyde achieves preferable technical effect up to 99.9%.
The present invention will be further described below by way of examples, but these embodiments are not anyway to this hair Bright range is construed as limiting.
Specific embodiment
[embodiment 1]
1, catalyst preparation
In terms of weight proportion, Al2O3: Ru:Sn is that 97:1:2 prepares catalyst.
By 97 parts of Al2O3Catalyst carrier is impregnated in the RuCl for being equivalent to 1 part of Ru at room temperature3With the SnCl of 2 parts of Sn4's RuCl3-SnCl4In 100 parts of mixed aqueous solution overnight, 80 DEG C after drying 12 hours, (hydrogen content is under 300 DEG C of hydrogen atmospheres The hydrogen nitrogen mixture of 4v%) reduction 4 hours, obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 2]
1, catalyst preparation
In terms of weight proportion, Al2O3: Pd:Sn is that 97:1:2 prepares catalyst.
By 97 parts of Al2O3Catalyst carrier is impregnated in the PdCl for being equivalent to 1 part of Pd at room temperature2With the SnCl of 2 parts of Sn4's PdCl2-SnCl4In 100 parts of mixed aqueous solution overnight, 80 DEG C after drying 12 hours, (hydrogen content is under 300 DEG C of hydrogen atmospheres The hydrogen nitrogen mixture of 4v%) reduction 4 hours, obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 3]
1, catalyst preparation
In terms of weight proportion, Al2O3: Pt:Sn is that 97:1:2 prepares catalyst.
By 97 parts of Al2O3Catalyst carrier is impregnated in the H for being equivalent to 1 part of Pt at room temperature2PtCl6With the SnCl of 2 parts of Sn4's H2PtCl6-SnCl4In 100 parts of mixed aqueous solution overnight, 80 DEG C after drying 12 hours, (the hydrogen content under 300 DEG C of hydrogen atmospheres For the hydrogen nitrogen mixture of 4v%) reduction 4 hours, obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 4]
1, catalyst preparation
In terms of weight proportion, Al2O3: Pt:Sn is that 97:1:2 prepares catalyst.
By 97 parts of Al2O3Catalyst carrier is impregnated in the H for being equivalent to 1 part of Pt at room temperature2PtCl6Mistake in 100 parts of aqueous solution At night, 80 DEG C after drying 12 hours, roast 4 hours under 400 DEG C of air atmospheres, obtain catalyst precursor B-04.B-04 is soaked Stain is in the SnCl for being equivalent to 2 parts of Sn4In 100 parts of aqueous solution overnight, 80 DEG C after drying 12 hours, (the hydrogen under 300 DEG C of hydrogen atmospheres Gas content is the hydrogen nitrogen mixture of 4v%) reduction 4 hours, obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 5]
1, catalyst preparation
In terms of weight proportion, Al2O3: Pt:Sn is that 97:1:2 prepares catalyst.
By 97 parts of Al2O3Catalyst carrier is impregnated in the SnCl for being equivalent to 2 parts of Sn at room temperature4In 100 parts of aqueous solution overnight, 80 DEG C after drying 12 hours, roast 4 hours under 400 DEG C of air atmospheres, obtain catalyst precursor B-05.B-05 is impregnated in It is equivalent to the H of 1 part of Pt2PtCl6In 100 parts of aqueous solution overnight, 80 DEG C after drying 12 hours, (the hydrogen under 300 DEG C of hydrogen atmospheres Content is the hydrogen nitrogen mixture of 4v%) reduction 4 hours, obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 6]
1, catalyst preparation
In terms of weight proportion, SiO2: Pt:Sn is that 97:1:2 prepares catalyst.
By 97 parts of SiO2Catalyst carrier is impregnated in the SnCl for being equivalent to 2 parts of Sn at room temperature4In 100 parts of aqueous solution overnight, 80 DEG C after dry 12 hours, is roasted 4 hours under 400 DEG C of air atmospheres, obtain catalyst precursor B-06.B-06 is impregnated in phase When in the H of 1 part of Pt2PtCl6In 100 parts of aqueous solution overnight, 80 DEG C after drying 12 hours, (hydrogen contains under 300 DEG C of hydrogen atmospheres Amount is the hydrogen nitrogen mixture of 4v%) reduction 4 hours, obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 7]
In terms of weight proportion, TiO2: Pt:Sn is that 97:1:2 prepares catalyst.
By 97 parts of TiO2Catalyst carrier is impregnated in the SnCl for being equivalent to 2 parts of Sn at room temperature4In 100 parts of aqueous solution overnight, 80 DEG C after dry 12 hours, is roasted 4 hours under 400 DEG C of air atmospheres, obtain catalyst precursor B-07.B-07 is impregnated in phase When in the H of 1 part of Pt2PtCl6In 100 parts of aqueous solution overnight, 80 DEG C after drying 12 hours, (hydrogen contains under 300 DEG C of hydrogen atmospheres Amount is the hydrogen nitrogen mixture of 4v%) reduction 4 hours, obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 8]
In terms of weight proportion, ZrO2: Pt:Sn is that 97:1:2 prepares catalyst.
By 97 parts of ZrO2Catalyst carrier is impregnated in the SnCl for being equivalent to 2 parts of Sn at room temperature4In 100 parts of aqueous solution overnight, 80 DEG C after dry 12 hours, is roasted 4 hours under 400 DEG C of air atmospheres, obtain catalyst precursor B-08.B-08 is impregnated in phase When in the H of 1 part of Pt2PtCl6In 100 parts of aqueous solution overnight, 80 DEG C after drying 12 hours, (hydrogen contains under 300 DEG C of hydrogen atmospheres Amount is the hydrogen nitrogen mixture of 4v%) reduction 4 hours, obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 9]
In terms of weight proportion, Al2O3: Pt:Cu is that 97:1:2 prepares catalyst.
By 97 parts of Al2O3Catalyst carrier is impregnated in the Cu (NO for being equivalent to 2 parts of Cu at room temperature3)2Mistake in 100 parts of aqueous solution At night, 80 DEG C after drying 12 hours, roast 4 hours under 400 DEG C of air atmospheres, obtain catalyst precursor B-09.B-09 is soaked Stain is in the H for being equivalent to 1 part of Pt2PtCl6In aqueous solution overnight, 80 DEG C after drying 12 hours, (hydrogen contains under 300 DEG C of hydrogen atmospheres Amount is the hydrogen nitrogen mixture of 4v%) reduction 4 hours, obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 10]
In terms of weight proportion, Al2O3: Pt:Cu:Sn is that 97:1:1.2:0.8 prepares catalyst.
By 97 parts of Al2O3Catalyst carrier is impregnated in the SnCl for being equivalent to 0.8 part of Sn at room temperature4With the Cu of 1.2 parts of Cu (NO3)2In 100 parts of aqueous solution overnight, it 80 DEG C after drying 12 hours, is roasted 4 hours under 400 DEG C of air atmospheres, obtains catalyst Precursor B-10.B-10 is impregnated in the H for being equivalent to 1 part of Pt2PtCl6In aqueous solution overnight, in 300 DEG C of hydrogen after 80 DEG C of dryings (the hydrogen nitrogen mixture that hydrogen content is 4v%) reduction 4 hours, obtain catalyst under atmosphere.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 11]
1, catalyst preparation
In terms of weight proportion, Al2O3: Pt is that 97:3 prepares catalyst.
By 97 parts of Al2O3Catalyst carrier is impregnated in the H for being equivalent to 3 parts of Pt at room temperature2PtCl6Mistake in 100 parts of aqueous solution At night, 80 DEG C after drying 12 hours, (the hydrogen nitrogen mixture that hydrogen content is 4v%) reduction 4 is small under 300 DEG C of hydrogen atmospheres When, obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 12]
1, catalyst preparation
In terms of weight proportion, Al2O3: Sn is that 97:3 prepares catalyst.
By 97 parts of Al2O3Catalyst carrier is impregnated in the SnCl for being equivalent to 3 parts of Sn at room temperature4In 100 parts of aqueous solution overnight, 80 DEG C after drying 12 hours, (the hydrogen nitrogen mixture that hydrogen content is 4v%) reduction 4 hours under 300 DEG C of hydrogen atmospheres, Obtain catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
[embodiment 13]
1, catalyst preparation
In terms of weight proportion, Al2O3: Cu is that 97:3 prepares catalyst.
By 97 parts of Al2O3Catalyst carrier is impregnated in the Cu (NO for being equivalent to 3 parts of Cu at room temperature3)2Mistake in 100 parts of aqueous solution At night, (the hydrogen nitrogen mixture that hydrogen content is 4v%) restores 4 hours under 300 DEG C of hydrogen atmospheres after 80 DEG C of dryings, obtains Catalyst.The formula of catalyst is shown in Table 1.
2, evaluating catalyst
Using industrial acrylic acid wastewater as raw material, Formaldehyde In Wastewarter 11082mg/L.Pass through after waste water and oxygen mix It is filled with the 125mL fixed bed reactors of 120g catalyst.Reaction temperature in reactor is 180 DEG C, pressure 4MPa, is stopped Time is 30 minutes.Reaction result is shown in Table 2.
The formula of 1. catalyst of table
Embodiment Method for preparing catalyst Catalyst formulation Each component quality proportioning
Embodiment 1 Method one Al2O3:Ru:Sn 97:1:2
Embodiment 2 Method one Al2O3:Pd:Sn 97:1:2
Embodiment 3 Method one Al2O3:Pt:Sn 97:1:2
Embodiment 4 Method two Al2O3:Pt:Sn 97:1:2
Embodiment 5 Method three Al2O3:Pt:Sn 97:1:2
Embodiment 6 Method three SiO2Pt:Sn 97:1:2
Embodiment 7 Method three TiO2:Pt:Sn 97:1:2
Embodiment 8 Method three ZrO2:Pt:Sn 97:1:2
Embodiment 9 Method three Al2O3:Pt:Cu 97:1:2
Embodiment 10 Method three Al2O3:Pt:Cu:Sn 97:1:1.2:0.8
Embodiment 11 -- Al2O3:Pt 97:3
Embodiment 12 -- Al2O3:Sn 97:3
Embodiment 13 -- Al2O3:Cu 97:3
2. reaction result of table

Claims (9)

  1. It, will be described useless 1. the wet oxidation processing method of formaldehyde-containing wastewater, is included in the presence of wet oxidation heterogeneous catalyst Water and oxygenous oxidant react the formaldehyde removed in waste water, the wet oxidation heterogeneous catalyst, with weight in the reactor Measure part meter, including following components:
    (1) 90~99.5 part of catalyst carrier；
    (2) 0.1~5 parts selected from least one of platinum family noble metal.
  2. 2. wet oxidation processing method according to claim 1, it is characterized in that the oxidant is air or oxygen.
  3. 3. wet oxidation processing method according to claim 1, it is characterized in that the temperature of reaction is 120~200 DEG C.
  4. 4. wet oxidation processing method according to claim 1, it is characterized in that reaction pressure is 2~5MPa.
  5. 5. wet oxidation processing method according to claim 1, it is characterized in that the residence time of waste water is 5~60 minutes.
  6. 6. wet oxidation processing method according to claim 1, it is characterized in that the catalyst carrier is selected from TiO2、 ZrO2、SiO2And Al2O3One of.
  7. 7. wet oxidation processing method according to claim 1, it is characterized in that the noble metal is selected from Ru, Pd, Pt, Ir At least one of with Rh.
  8. 8. wet oxidation processing method according to claim 1, it is characterized in that the content of formaldehyde of the formaldehyde-containing wastewater is 100~20,000mg/L.
  9. 9. wet oxidation processing method described in claim 1, it is characterized in that the wet oxidation heterogeneous catalyst is using including It is prepared by the preparation method of following steps:
    1) compound solution containing precious metal element is mixed with carrier；
    2) the compound state noble metal for introducing step 1) is simple substance.
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