JP4703227B2 - Wastewater treatment method - Google Patents

Description

  The present invention relates to alkaline waste water (hereinafter simply referred to as “waste water”) containing a high concentration of at least one of nitrogen compounds, organic substances and inorganic substances (hereinafter sometimes simply referred to as “polluting components”). )).

  A method of performing wet oxidation treatment and / or catalytic wet oxidation treatment of waste water containing at least one of nitrogen compounds, organic substances and inorganic substances is known. For example, Patent Document 1 by the present applicant discloses “a method for decomposing ammonia, organic substances and inorganic substances in wastewater by subjecting the wastewater to catalytic wet oxidation in the presence of a supported catalyst”. Yes. As is apparent from the results shown in the examples, this method can generally exhibit a very excellent wastewater treatment effect.

  However, in this method, when the concentration of pollutant components in the wastewater is high (for example, when the CODcr concentration is 75 g / L-TOD concentration is 83 g / L- or more), a relatively large amount of air (oxygen) is used. Then, when the treatment is performed under high temperature and high pressure conditions, a large amount of water evaporates in the reaction tower and shifts to the gas phase. Therefore, in order to cope with the temperature decrease due to latent heat of vaporization, external heating is required during operation, it becomes difficult to maintain the liquid phase state well and the reaction is continued, and the removal rate of polluted components decreases. There is.

Also, often the amount of evaporation of pollutant component concentration is high liquid in the waste water, the metal components in the waste water, the metal salt (metal oxides, etc.), carbonates (Na ₂ CO _3, etc.), sulfate (Na ₂ SO ₄ Etc.), the metal component in the wastewater adheres to the surface of the support and / or the catalyst and its activity is lowered, and the treatment may not be performed well.

Also, when the organic matter (TOC) concentration and / or the total concentration of sulfur compounds are high in the pollutant components in the alkaline wastewater, it is due to precipitation of alkali salts, sulfur salts, etc. in the wet oxidation treatment and / or catalytic wet oxidation treatment system. Occasional blockage may result in poor operation.
Japanese Patent Publication No.59-29317

  Therefore, the present invention is an effective and stable wet oxidation treatment and / or catalytic wet oxidation treatment (hereinafter referred to as “oxidation”) which efficiently and stably contains alkaline wastewater containing a high concentration of at least one of nitrogen compounds, organic substances and inorganic substances. It is an object to provide a method that may be collectively referred to as “processing”.

Specifically, the present invention suppresses liquid evaporation in the processing system, does not require external heating during operation, can maintain the liquid phase state well, and can continue the reaction. It aims to provide a new oxidation treatment method that can stably operate without clogging with salt compounds, etc., can effectively treat wastewater with high concentration of pollutants, and suppresses CO ₂ emission to the atmosphere. .

  As a result of intensive studies in view of the current state of the technology as described above, the inventor circulated and mixed a part of the liquid phase after the oxidation treatment with the waste water before the treatment, and / or It has been found that the above-mentioned problems can be achieved by mixing exhaust gas after oxidation treatment with waste water before treatment to precipitate salts and oxidizing the alkaline waste liquid after removing the salts. Based on this knowledge, further studies have been made and the present invention has been completed.

  That is, the present invention provides the following wastewater treatment method.

Item 1. A method of subjecting alkaline wastewater containing a high concentration of at least one of a nitrogen compound, an organic substance and an inorganic substance to a wet oxidation treatment and / or a catalytic wet oxidation treatment under conditions of 100 ° C. or higher and 0.5 MPa or higher. ,
(1) A part of the liquid phase obtained by separating the gas-liquid after the wet oxidation treatment and / or catalytic wet oxidation treatment in accordance with the CODcr concentration in the alkaline wastewater before the treatment is converted into the alkaline wastewater before the treatment. A step of circulating and / or
(2) The exhaust gas obtained by separating the gas-liquid after the wet oxidation treatment and / or the catalyst wet oxidation treatment is mixed with the alkaline waste water before the treatment to precipitate the salts, and after separating the salts, the alkaline waste water A method for treating alkaline wastewater, comprising a step of wet oxidation treatment and / or catalytic wet oxidation treatment.

Item 2. In step (1), the treatment amount of alkaline waste water before treatment is W ₀ (kg / hr), the circulation amount of a part of the liquid phase obtained by gas-liquid separation is W ₁ (kg / hr), and the treatment amount before treatment When the CODcr concentration in the alkaline waste water is X (g / L) and the relative amount of W ₁ with respect to W ₀ is Y (= W ₁ / W ₀ ), in the correlation diagram of Y and X, Y is the formula Item 2. The method for treating alkaline wastewater according to Item 1, wherein the method is within the range represented by Formula 1 and Formula 2.
Y ¹ = X / 100 (Formula 1)
Y ² = X / 33 (Formula 2)
Item 3. Total amount of exhaust gas obtained by separating the gas-liquid after wet oxidation treatment and / or catalytic wet oxidation treatment when the TOC concentration in alkaline wastewater before treatment is 15 g / L or more or the total concentration of sulfur compounds is 30 g / L or more Item 2. The method for treating alkaline wastewater according to Item 1, wherein the wastewater is mixed with alkaline wastewater before treatment.

  The present invention is described in detail below.

  The wastewater to be treated by the present invention is not particularly limited as long as it is alkaline wastewater containing a high concentration of pollutant components such as nitrogen compounds, organic substances, and inorganic substances. Here, the high concentration means a concentration in which the CODcr concentration in the wastewater is 20 g / L or more, particularly 30 g / L or more, and the alkalinity of the alkaline wastewater means about pH 8-14. In addition, even if it is a case where pH of wastewater is not said range, what is necessary is just to adjust suitably so that pH may become said range by a well-known method. For example, the pH may be adjusted using sodium hydroxide, potassium hydroxide, sodium carbonate or the like.

Nitrogen compounds contained in wastewater include NH ₄ -N (ammonium nitrogen), NO ₂ -N (nitrite nitrogen), NO ₃ -N (nitrate nitrogen), organic nitrogen (including amines) ), Inorganic nitrogen (including CNs and SCNs) and the like.

  Organic substances contained in wastewater include general organic substances (phenols, alcohols, aldehydes, carboxylic acids, etc.), organic chlorine compounds (trichloroethylene, tetrachloroethylene, dioxins, etc.) , Suspended solids (derived from organic solid waste, sludge generated from various biological treatment processes, soot, municipal waste, biomass, etc.).

Examples of the inorganic substance contained in the wastewater include general inorganic substances (for example, S ₂ O ₃ ²⁻ , SO ₃ ²⁻ , SCN ⁻ , CN ^{− and the} like).

  The various wastewaters to be treated by the present invention include wastewater containing one of the above nitrogen compounds, organic substances and inorganic substances, or a combination of two or more of these. The wastewater that is present.

  Examples of such wastewater include wastewater (gas liquid) generated in a coal processing coke oven plant, coal gasification plant, coal liquefaction plant, etc., wastewater generated by gas generation in these plants, wet Wastewater from desulfurization towers and wet desiccant towers, photographic wastewater, printing wastewater, agricultural chemicals-related wastewater, dyeing wastewater, semiconductor manufacturing plant wastewater, organic synthetic chemical plant wastewater, petrochemical factory wastewater, oil refinery factory wastewater, pharmaceutical factory wastewater, papermaking Occurring due to biological treatment (anaerobic treatment, aerobic treatment) of industrial wastewater, industrial wastewater, wastewater generated from the thermal decomposition of industrial wastewater, wastewater generated from wastewater generated from chemical factory wastewater, waste, paper, plastics, etc. Sludge, sewage sludge, wastewater generated from sewage sludge liquefaction, wastewater containing organochlorine compounds, various cyanogen-containing wastewater discharged from the plating industry, soft nitrogen of steels Process, liquid carburization, cyan liquid used in the surface treatment such as chemical conversion treatment, such as cyan waste liquid discharged from these surface treatment processes are exemplified.

  In addition to the nitrogen compounds, organic substances (TOC, etc.) and inorganic substances in the waste water, the present invention further includes Mg, Al, Si, P, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn. It is also useful for treating waste water or sludge containing one or more metal components such as Cd.

The present invention is a method for performing wet oxidation treatment and / or catalytic wet oxidation treatment on the above alkaline waste water under the conditions of 100 ° C. or more and 0.5 MPa or more, and is a treatment method or treatment system including the following steps. It is characterized by.
(1) A part of the liquid phase obtained by separating the gas-liquid after the wet oxidation treatment and / or catalytic wet oxidation treatment in accordance with the CODcr concentration in the alkaline wastewater before the treatment is converted into the alkaline wastewater before the treatment. A step of circulating and / or
(2) The exhaust gas obtained by separating the gas-liquid after the wet oxidation treatment and / or the catalyst wet oxidation treatment is mixed with the alkaline waste water before the treatment to precipitate the salts, and after separating the salts, the alkaline waste water A step of wet oxidation treatment and / or catalytic wet oxidation treatment.

  In the step (1), a part of the liquid phase obtained after the gas-liquid separation is circulated and mixed with the raw wastewater introduced into the reaction system, for example, at the oxidation treatment heater inlet and / or the reactor inlet. .

  In addition, as a method of taking out a part of the liquid phase after the oxidation treatment, a method using the liquid phase portion from the lower part of the gas-liquid separator at the high temperature and high pressure provided at the oxidation reaction tower outlet, or after the oxidation treatment A method using a liquid phase part from the lower part of the gas-liquid separator after passing through the cooler is used.

  According to this step (1), a part of the liquid phase obtained after the gas-liquid separation is circulated and mixed with the alkali waste liquid before the treatment, so that the liquid evaporation in the treatment system can be suppressed and the oxidation reaction tower. The liquid linear velocity can be maintained. In addition, there is an advantage that external heating is not required during operation, and the oxidation process can be performed while maintaining a good liquid phase state. Furthermore, since the evaporation of the liquid can be suppressed, the concentration of the metal component and its salt in the wastewater does not increase, and metal adhesion and adsorption on the catalyst surface can be reduced, so that the catalytic activity can be maintained.

Here, the treatment amount of the alkaline waste water before the treatment introduced into the reaction system is W ₀ (kg / hr), the partial circulation amount of the liquid phase after the gas-liquid separation is W ₁ (kg / hr), and When the CODcr concentration in the alkaline waste water before treatment is X (g / L) and the relative amount of W ₁ with respect to W ₀ is Y (= W ₁ / W ₀ ), In the correlation diagram of Y and X, it is preferable that Y is within the range represented by Equation 1 and Equation 2. (See FIG. 4).
Y ¹ = X / 100 (Formula 1)
Y ² = X / 33 (Formula 2)
In such a range, a part of the liquid phase after gas-liquid separation is circulated and mixed with the alkali waste water before the treatment, so that even if a relatively large amount of air (oxygen) is used and the oxidation treatment is performed under high temperature and high pressure conditions, Evaporation can be suppressed, the reaction can be continued without requiring external heating and maintaining a good liquid phase state.

  Here, in the correlation diagram of Y and X, when Y is smaller than that shown in Equation 1, the dissolution of the contaminating component in the alkaline waste liquid before the treatment becomes insufficient, and the contaminating component is precipitated or precipitated in the reaction system. This is not preferable. On the other hand, when Y is larger than that shown in Formula 2, it is a waste liquid self-combustion region, and not only does the effect of the present invention be affected by circulating the liquid phase after excessive gas-liquid separation, but also the cost. Is not preferred because of an increase in

In particular, in the correlation diagram of Y and X, it is more preferable that Y is within the range represented by Equation 3 and Equation 4 (FIG. 4). This is because the above-described effects of the present invention are more suitably exhibited within this range.
Y ³ = X / 84 (Formula 3)
Y ⁴ = X / 42 (Formula 4)
Further, if the CODcr concentration (g / L) in the alkaline wastewater before the treatment indicated by X is usually 20 or more, the above relationship applies. Specifically, if X is 30 or more, 40 or more, about 50 to 500, particularly about 70 to 350, the above relationship is preferably applied.

  In the step (2), the exhaust gas obtained by separating the gas-liquid after the wet oxidation treatment and / or the catalyst wet oxidation treatment is introduced into the alkaline waste water before the treatment to precipitate salts. Thereafter, the precipitated salts are separated by settling, and the alkali waste water (liquid phase) after separation is subjected to wet oxidation treatment and / or catalytic wet oxidation treatment. The method of introducing the exhaust gas into the raw waste water is not particularly limited, and a method such as a gas-liquid contact method or bubbling may be adopted by returning the exhaust gas to the raw waste water in its entirety. As the gas-liquid contact method, either a batch type or a flow type may be adopted.

  The exhaust gas after oxidation treatment contains carbon dioxide gas from the decomposition of organic matter, and it reacts with alkali metal ions, alkaline earth metal ions, etc. present in the wastewater by introducing it into the alkaline waste water before treatment. Then, insoluble carbonates, sulfates, metal salts, and other salts are formed, resulting in precipitation. In this way, by actively removing the alkali components and metal components present in the raw waste liquid, it is possible to efficiently treat the waste water while suppressing the decrease in the catalytic activity, and to prevent the precipitation of salts in the reaction system and to be stable. Oxidation treatment is possible.

  In particular, when the TOC concentration in the alkaline waste water before treatment is 15 g / L or more (especially 20 g / L or more) or the total concentration of sulfur compounds is 30 g / L or more (especially 35 g / L or more), the above effect is obtained. It will be remarkable.

  The wet oxidation and catalytic wet oxidation in the present invention can be carried out using known reaction conditions, except for the above step (1) and step (2).

  For example, the wet oxidation reaction tower is filled with an empty tower or several trays or supports. The support is filled with at least one selected from alumina, silica, zirconia, titania, and composite metal oxides containing these metal oxides (alumina-silica, alumina-silica-zirconia, titania-zirconia, etc.). .

  The catalyst wet oxidation reaction tower is packed with a catalyst. The catalytically active component of the catalyst is at least one selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, copper, gold and tungsten, and water-insoluble or hardly soluble compounds of these metals. More than seeds are filled. Alternatively, a composite catalyst in which metals La, Ce, and Te are further mixed as a catalytically active component is used.

  As the catalyst carrier, the carrier used in the wet oxidation reaction tower, that is, alumina, silica, zirconia, titania, composite metal oxides containing these metal oxides (alumina-silica, alumina-silica-zirconia, titania-zirconia, etc.) At least one selected from the above) is used.

  Alternatively, a composite carrier in which metal La, Ce, Te or the like is further mixed is used.

  The supported catalyst used for the catalyst wet oxidation is not particularly limited, and examples thereof include a spherical shape, a pellet shape, a cylindrical shape, a crushed piece shape, a powder shape, and a honeycomb shape.

Reactor volume when filled using such supported catalysts, in the case of a fixed bed, the spatial velocity 0.5～10Hr ^-1 order of the liquid, more preferably to such a degree 1～5Hr ^-1 Is good.

  The size of the supported catalyst used in the fixed bed is usually about 3 to 50 mm, more preferably about 4 to 25 mm in the case of a spherical shape, a pellet shape, a cylindrical shape, a crushed piece shape, a powder shape and the like.

The physical properties of the support or catalyst (supported catalyst) are preferably a packing density of 1.2 g / ml or more, a specific surface area of 10 m ² / g or more, a pore volume of 0.10 ml / g or more, and a crushing strength of 100 N or more.

  In addition, as a honeycomb structure when the catalyst is supported on a honeycomb-shaped carrier, an opening having an arbitrary shape such as a square, a hexagon, or a circle is used.

The area per unit volume, the aperture ratio, and the like are not particularly limited, but usually an area per unit volume of about 200 to 800 m ² / m ³ and an aperture ratio of about 40 to 80% may be used.

  Examples of the material of the honeycomb structure include metal oxides and metals similar to those described above, and zirconia, titania and titania-zirconia having excellent durability are more preferable.

  The amount of the catalytically active component supported on the carrier is usually about 0.05 to 25% by weight, more preferably about 0.3 to 3% by weight.

  Here, the wet oxidation treatment and / or the catalytic wet oxidation treatment are performed under the conditions that the temperature in the reaction tower is 100 ° C. or more, the pressure is 0.5 MPa or more, and further 1 MPa or more. In particular, when the temperature is about 150 to 350 ° C., particularly about 200 to 300 ° C., and the pressure is about 1 to 20 MPa, particularly about 2 to 15 MPa, the effect of the present invention is effectively exhibited.

  The higher the temperature and pressure during the reaction and the higher the oxygen fraction of the oxygen-containing gas, the higher the decomposition and removal rate of the pollutant components, and the shorter the waste water residence time in the reaction tower, the less the required amount of catalyst. As the equipment and power costs increase, the reaction temperature and pressure should be comprehensively considered within the above range, including the concentration of pollutant components in the wastewater, the required treatment level, operating costs, and construction costs. Determined.

  The pressure during the reaction may be 0.5 MPa or more, further 1 MPa or more, and may be any pressure that allows the treated wastewater to maintain a liquid phase at the reaction temperature. Here, the “pressure at which the liquid phase can be maintained” refers to the amount of liquid (waste water), water vapor, and gas (steam The amount of water vapor is 60% or less (more preferably 50% or less) and the pressure inside the reaction tower is substantially maintained in the liquid phase.

  The amount of oxygen supplied to the reaction tower is more than the theoretical oxygen amount necessary for decomposing nitrogen compounds, organic substances and inorganic substances into harmless products, more preferably 1 to 3 times the theoretical oxygen amount. The amount is about 1.05 to 1.5 times the theoretical oxygen amount.

Examples of the oxygen source include air, oxygen-enriched air (oxygen-enriched air obtained using a selective oxygen-permeable membrane, air-oxygen mixture, and oxygen-enriched air obtained by treating air with a PSA apparatus. Etc.), oxygen, and substances capable of generating oxygen under wastewater treatment conditions (O ₃ , H ₂ O _2, etc.) can be used.

  As the oxygen source, an oxygen-containing waste gas containing one or more of hydrogen cyanide, hydrogen sulfide, ammonia, sulfur oxide, organic sulfur compound, nitrogen oxide, hydrocarbon and the like as impurities may be used. According to the present invention, impurities in these oxygen sources are also decomposed together with the components to be treated in the wastewater.

According to the present invention, when a high-concentration oxygen-containing gas (e.g., pure oxygen) is used, wastewater treatment can be performed in a time of minutes in a relatively low pressure condition of 10 kg / cm ² (0.98 MPa) or less. It can be carried out.

Also, when performing wet oxidation and / or catalytic wet oxidation wastewater treatment under subcritical, critical or supercritical conditions using an oxygen-containing gas (such as H ₂ O ₂ ), operate in seconds. Can be completed.

In the present invention, “theoretical oxygen amount” means “nitrogen compounds, organic substances and inorganic substances (treated components) in wastewater into harmless products (N ₂ , H ₂ O and CO ₂ ). Means the amount of oxygen necessary for decomposition. The theoretical oxygen amount can be easily determined by analyzing the components to be treated in the wastewater to be treated and calculating the amount of oxygen necessary for their decomposition. Practically, it is possible to find a relational expression for approximately calculating the theoretical oxygen amount with high accuracy using several parameters based on experience and experiment. An example of such a relational expression is described in Japanese Patent Publication No. 58-27999.

  In the heat exchanger, heat recovery is performed by circulating a high-temperature gas-liquid phase from the wet oxidation reaction tower and / or the catalytic wet oxidation reaction tower.

  In addition, when the predetermined reaction temperature cannot be maintained during the reaction due to heat dissipation in winter, etc., or when it is necessary to raise the temperature to the predetermined temperature, heat medium oil circulation (not shown) or fuel from the outside The temperature can be raised by a heater such as by heating (not shown), or steam from a steam generator (not shown) can be used.

  Further, high-pressure steam can be directly supplied to the wet oxidation reaction tower and / or the catalyst wet oxidation reaction tower.

  In addition, at the time of start-up, in order to set the temperature in the reaction tower to a predetermined temperature, in addition to raising the temperature by directly sending steam to the reaction tower, by decomposing easily decomposable substances such as methanol after reaching the predetermined temperature The temperature can also be raised by raising the temperature using reaction heat or the like.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a flow sheet showing an outline of the present invention, and is a diagram showing an example of a processing step in which a wet oxidation reaction tower 9 and a catalytic wet oxidation reaction tower 109 are provided.

  The waste water is boosted from the raw waste water tank 1 to a predetermined pressure by the boost pump 3 and further mixed with the oxygen-containing gas whose pressure is increased by the compressor 21. Next, after being heated to a predetermined temperature by the heat exchanger 5 and, if necessary, the heater 7, it is supplied to the wet oxidation reaction tower 9. After the gas and liquid exiting the wet oxidation reaction tower 9 pass through the heat exchanger 5 and, if necessary, the cooler 30, the gas and liquid are separated into exhaust gas and treated water by the gas and liquid separator 16. The exhaust gas containing carbon dioxide gas is introduced into the raw waste water tank 1 where it reacts with alkali in the raw waste water to produce precipitates such as carbonates, sulfates and metal salts. The precipitate is appropriately extracted from the lower part of the tank 1. Further, as described above, the treated water is circulated and mixed with the raw water in accordance with the CODcr concentration in the wastewater before treatment.

  Further, the pressure is increased from the wet-oxidized water tank 101 to a predetermined pressure by the pump 103 and further mixed with the oxygen-containing gas that has been increased by the compressor 21. Next, after being heated to a predetermined temperature by the heat exchanger 105 and, if necessary, the heater 107, the heat is supplied to the catalytic wet oxidation reaction tower 109. The gas-liquid exiting the catalyst wet oxidation reaction tower 109 passes through the heat exchanger 105 and the cooler 130, and is then gas-liquid separated into exhaust gas and treated water by the gas-liquid separator 116. The exhaust gas containing carbon dioxide gas is introduced into the raw waste water tank 1 where it reacts with alkali in the raw waste water to produce precipitates such as carbonates, sulfates and metal salts. The precipitate is appropriately extracted from the lower part of the tank 1. Further, as described above, the treated water is circulated and mixed with the raw water according to the CODcr concentration in the waste water before treatment (the waste water after the wet oxidation treatment, that is, the waste water in 102).

  In addition to the above, gas-liquid separation after the wet oxidation treatment and / or the catalytic wet oxidation treatment can be performed under high temperature and high pressure at the outlet of the wet oxidation reaction tower 9 or the catalytic wet oxidation reaction tower 109. Treated water can also be circulated.

  At least a part of each treated water obtained by each gas-liquid separator 16 or 116 in FIG. 1 passes through the liquid circulation line 20 or 120 and the circulation pump 50 or 150, and the line before each booster pump 3 or 103. Returned to

The liquid phase circulation rate W ₁ (kg / hr) after gas-liquid separation depends on the nature of the raw wastewater (types of components to be treated and their concentrations, etc.), the degree of decrease in activity of the catalyst charged in the reactor, etc. The amount is usually about 0.1 to 10 times, more preferably about 1 to 6 times the amount of waste water W ₀ (kg / hr). When the relative amount of W ₁ with respect to W ₀ is Y (= W ₁ / W ₀ ), Y can be determined according to the CODcr concentration in the alkaline wastewater. In the correlation diagram, it is preferable that Y is within a range represented by Formula 1 and Formula 2 (particularly Formula 3 and Formula 4).

Here, the treatment amount of the alkaline waste water before the treatment introduced into the reaction system is W ₀ (kg / hr), the circulation amount of the liquid phase after the gas-liquid separation is W ₁ (kg / hr), and the alkaline waste water. In the method for treating alkaline wastewater according to the present invention, when the CODcr concentration of X is set to X (g / L) and the relative amount of W _{1 to} W ₀ is set to Y (= W ₁ / W ₀ ), the correlation between Y and X In the figure, Y is in the range indicated by Formula 1 and Formula 2 (particularly Formula 3 and Formula 4) (see FIG. 4).

  The liquid linear velocity in the column is usually about 0.1 to 1.0 cm / sec, more preferably about 0.2 to 0.9 cm / sec in order to perform catalyst washing while forming a fixed bed in the reaction column.

  The gas linear velocity is automatically determined by maintaining the above-mentioned liquid linear velocity in the column and the “theoretical oxygen amount” from the CODcr concentration (or TOD concentration) of the raw waste water.

  The ratio of mixing exhaust gas after wet oxidation treatment and / or catalytic wet oxidation treatment with waste water before treatment corresponds to the TOC concentration, alkali concentration, sulfur salt concentration of waste water, all or part is returned, gas-liquid contact method May be batch and / or flow-through.

  In addition, the inside of the system may be washed with an acid or alkali solution irregularly. The cleaning solution in the system in the wet oxidation treatment and / or the catalyst wet oxidation treatment in the present invention, the regeneration (washing) treatment solution of the catalyst wet reaction tower packed catalyst to be used, the metal component in the liquid by coagulation precipitation treatment etc. if necessary After the removal, the wet oxidation treatment and / or catalytic wet oxidation treatment with waste water can be performed by the method of the present invention.

  The regeneration of the catalyst is not particularly limited, but for example, a gas-liquid mixed phase of an acid aqueous solution and air and / or a gas-liquid mixed phase of an alkaline aqueous solution and air and / or an acid aqueous solution, an alkaline aqueous solution and air. And a gas-liquid mixed phase with each other can be carried out by a washing process using them alternately.

  Examples of the acid aqueous solution include a nitric acid aqueous solution and an ascorbic acid aqueous solution. Examples of the alkali aqueous solution include a sodium hydroxide aqueous solution. Water washing is performed between the acid aqueous solution and the alkaline aqueous solution washing.

  FIG. 2 is a diagram illustrating an example of processing steps including the wet oxidation reaction tower 9.

  The treated liquid in the wet oxidation reaction tower 9 is separated into a gas phase and a liquid phase by the first high-pressure / high-temperature gas-liquid separator 11. A part of the separated liquid phase is circulated through the flow path 12 (this circulation operation is referred to as “hot recycling”). As described above, the remaining gas / liquid is used as a heating source of waste water in the heat exchanger 5 and then sent to a cooler (not shown) as necessary, and further to the second gas / liquid separator 16. It is sent and separated into a gas phase (exhaust gas) and a liquid phase (treated water). The exhaust gas containing carbon dioxide gas is introduced into the raw waste water tank 1 through the flow path 18, where it reacts with alkali in the raw waste water to produce precipitates such as carbonates, sulfates and metal salts. The precipitate is appropriately extracted from the lower part of the raw waste water tank 1.

  FIG. 3 is a diagram illustrating an example of a processing process including the catalytic wet oxidation reaction tower 109.

  The treated liquid in the catalytic wet oxidation reaction tower 109 is separated into a gas phase and a liquid phase by the first high-pressure / high-temperature gas-liquid separator 111. A part of the liquid phase separated here is hot recycled through the flow path 112. As described above, the remaining gas / liquid is used as a heating source of waste water in the heat exchanger 105, and then sent to a cooler (not shown) as necessary, and further to the second gas / liquid separator 116. It is sent and separated into a gas phase (exhaust gas) and a liquid phase (treated water). Exhaust gas containing carbon dioxide is introduced into the raw wastewater tank 101 through the flow path 118, where it reacts with alkali in the raw wastewater to produce precipitates such as carbonates, sulfates, and metal salts. The precipitate is appropriately extracted from the lower part of the raw waste water tank 101.

  According to the present invention, when performing wet oxidation treatment and / or catalytic wet oxidation treatment of alkaline wastewater containing a high concentration of at least one of nitrogen compounds, organic substances and inorganic substances (contamination components), A part of the liquid phase obtained by gas-liquid separation after the catalyst wet oxidation treatment is circulated. This suppresses liquid evaporation and maintains the liquid linear velocity in the tower, so that external heating is required even when processing under high temperature and high pressure conditions using a relatively large amount of air (oxygen). The reaction can be continued while maintaining a good liquid phase state.

Furthermore, according to the present invention, the surface of the catalyst is prevented without increasing the concentration of metal components, carbonates (Na ₂ CO ₃ etc.), sulfates (Na ₂ SO ₄ etc.) in the wastewater by suppressing the evaporation of the liquid. In addition to reducing the amount of metal adhering to and adsorbing to the catalyst, the liquid film resistance of the catalyst surface can be reduced, improving catalyst activity and durability, and reducing wastewater without being restricted by the concentration of contaminating components. It can be processed efficiently.

In addition, exhaust gas after wet oxidation treatment and / or catalytic wet oxidation treatment is mixed with wastewater before treatment, and wastewater before treatment as carbonate (Na ₂ CO ₃ etc.), sulfate (Na ₂ SO ₄ etc.), etc. After the sedimentation and separation, the wet oxidation treatment and / or the catalytic wet oxidation treatment prevents precipitation of these salts during operation, and stable treatment is possible.

According to the present invention, when a high-concentration oxygen-containing gas (e.g., pure oxygen) is used, wastewater treatment can be performed in a time of minutes in a relatively low pressure condition of 10 kg / cm ² (0.98 MPa) or less. It can be carried out.

Also, when performing wet oxidation and / or catalytic wet oxidation wastewater treatment under subcritical, critical or supercritical conditions using an oxygen-containing gas (such as H ₂ O ₂ ), operate in seconds. Can be completed.

  Furthermore, according to the method of the present invention, each process is performed continuously, and the processing flow is extremely simple. Therefore, the processing cost (equipment cost, operating cost, etc.) is significantly reduced, and process management is facilitated.

  Examples and Comparative Examples are shown below to further clarify the features of the present invention.

Example 1
Wastewater (alkaline wastewater containing a high concentration of nitrogen-containing compounds, organic substances and inorganic substances) generated in an oil refinery having the properties shown in Table 1 was treated according to the flow shown in FIG.

The CODcr concentration of the raw wastewater was 275 g / L, the raw wastewater treatment amount was 105 kg / hr, and the air amount was 125 Nm ³ / hr. From the treated water tank 101, wet oxidized treated water was circulated and mixed with raw wastewater at a circulation rate of 347 kg / hr. This amount of circulation corresponds to about 3.3 times the amount of raw wastewater treated.

  The outlet temperature of the wet oxidation reactor 9 was 275 ° C., and the pressure was 9.75 MPa. At this time, the vapor ratio in the upper portion of the wet oxidation reactor 9 was about 50%. The reaction time was 1 hr.

Further, the wet oxidation treated water (CODcr concentration 65.9 g / L) thus obtained was subjected to catalytic wet oxidation treatment with a wastewater treatment amount of 108 kg / hr and an air amount of 35 Nm ³ / hr. In addition, in the catalyst wet oxidation treatment, the liquid circulation treatment of the catalyst wet oxidation treatment water from the treatment water tank 140 was not performed.

  The outlet temperature of the catalytic wet oxidation reactor 109 was 270 ° C., and the pressure was 9.75 MPa. The proportion of steam in the catalytic wet oxidation reactor 109 was about 43%. The reaction tower 109 was filled with a spherical catalyst (diameter: about 5 mm) in which 2% of the support weight of ruthenium was supported on a titania support (reaction time: 2 hours).

By these treatments, the catalyst wet oxidation treated water has a CODcr concentration of 1 g / L or less. CODcr and TOC removal rates in all steps of the above wet oxidation treatment and catalyst wet oxidation treatment were 99% or more. In addition, NH ₃ —N was not detected in the treated water.

In addition, exhaust gas after wet oxidation treatment and catalytic wet oxidation treatment is fully returned to the raw waste water and brought into gas-liquid counter-current contact, and after precipitation removal as alkali salts (Na ₂ CO ₃ etc.) and sulfur salts (Na ₂ SO ₄ etc.) It was possible to perform stable operation for a long time by processing. Of course, no precipitation or precipitation of salts was observed in the reaction system.

Comparative Example 1
The treatment was performed in the same manner as in Example 1 except that the exhaust gas after the wet oxidation treatment and the catalyst wet oxidation treatment was not circulated. As a result, pressure loss increases and becomes clogged due to precipitation of alkali salts (Na ₂ CO ₃ etc.) and sulfur salts (Na ₂ SO ₄ etc.) in pipes, heat exchangers, and reaction towers. became.

Comparative Example 2
In the wet oxidation treatment, the treatment was performed in the same manner as in Example 1 except that the circulation treatment from the wet oxidation treatment water tank was not performed. As a result, the CODcr concentration of the wet oxidation treated water is reduced by the temperature drop due to liquid evaporation in the wet oxidation reactor, and the precipitation of metal salt, alkali salt (Na ₂ CO ₃ etc.), sulfur salt (Na ₂ SO ₄ etc.). It rose significantly and was shut down in a short time.

Example 2
The wastewater generated in the oil refinery used in Example 1 (alkaline wastewater containing high concentrations of nitrogen-containing compounds, organic substances and inorganic substances) was diluted to a CODcr concentration of 100 g / L and a TOC concentration of 36 g / L. Then, aqueous ammonia was added to adjust the NH ₃ —N concentration to 3000 mg / L. This wastewater was treated according to the flow shown in FIG.

The raw wastewater treatment amount was 20.8 kg / hr and the air amount was 7.7 Nm ³ / hr. The catalyst wet oxidation treated water was circulated and mixed into the raw wastewater from the treated water tank at a circulation rate of 31 kg / hr. This amount of circulation corresponds to about 1.5 times the amount of raw wastewater treated. The reaction time was 0.75 hr.

The water quality after the treatment was CODCr: 100 mg / L, TOC: 35 mg / L NH ₃ -N: <1 mg / L.

  The reaction tower was filled with a spherical catalyst (diameter: about 5 mm) in which 2% of the support weight of ruthenium was supported on a titania support.

In addition, the exhaust gas after the catalyst wet oxidation treatment is fully returned to the raw waste water and brought into gas-liquid countercurrent contact, and after precipitating and removing it as alkali salts (Na ₂ CO ₃ etc.) and sulfur salts (Na ₂ SO ₄ etc.) The operation was stable for a long time.

It is a flow sheet which shows the outline of the wet oxidation treatment and catalyst wet oxidation treatment of the present invention. It is a flow sheet which shows the outline of the wet oxidation treatment of the present invention. It is a flow sheet which shows the outline of the catalyst wet oxidation treatment of the present invention. In the correlation diagram of X and Y, it is a graph which shows the relationship of Formula 1-4.

Explanation of symbols

1: Raw waste water tank 3: Booster pump 5: Heat exchanger 7: Heater 9: Wet oxidation reactor 11: High pressure / high temperature gas-liquid separator 16: Gas-liquid separator 17, 18: Wet oxidation treatment exhaust gas 19, 20 : Wet oxidation treated water 30: cooler 50: circulation pump 101: wet oxidation treated water tank 103: boost pump 105: heat exchanger 107: heater 109: catalytic wet oxidation reactor 111: high temperature / high pressure gas-liquid separator 116 : Gas-liquid separator 117, 118: Catalyst wet oxidation treatment exhaust gas 119, 120: Catalyst wet oxidation treatment treated water 121: Compressor 130: Cooler 140: Treated water tank 150: Circulation pump

Claims (2)

A method of subjecting alkaline wastewater containing a high concentration of at least one of a nitrogen compound, an organic substance and an inorganic substance to a wet oxidation treatment and / or a catalytic wet oxidation treatment under conditions of 100 ° C. or higher and 0.5 MPa or higher. ,
(1) A part of the liquid phase obtained by separating the gas-liquid after the wet oxidation treatment and / or catalytic wet oxidation treatment in accordance with the CODcr concentration in the alkaline wastewater before the treatment is converted into the alkaline wastewater before the treatment. Circulating and mixing , and
(2) The exhaust gas obtained by separating the gas-liquid after the wet oxidation treatment and / or the catalyst wet oxidation treatment is mixed with the alkaline waste water before the treatment to precipitate the salts, and after separating the salts, the alkaline waste water A method for treating alkaline wastewater, comprising a step of wet oxidation treatment and / or catalytic wet oxidation treatment. Total amount of exhaust gas obtained by separating the gas-liquid after wet oxidation treatment and / or catalytic wet oxidation treatment when the TOC concentration in alkaline wastewater before treatment is 15 g / L or more or the total concentration of sulfur compounds is 30 g / L or more The method for treating alkaline wastewater according to claim 1, wherein the wastewater is mixed with alkaline wastewater before treatment.

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