Classifications

• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
• • 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
  • C02F1/28—Treatment of water, waste water, or sewage by sorption
  • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
• • 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
  • C02F2101/32—Hydrocarbons, e.g. oil
  • C02F2101/325—Emulsions
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
  • C02F2103/322—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from vegetable oil production, e.g. olive oil production
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
  • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
  • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)

Definitions

• Adsorbent Adsorbent, method for producing the same, and method for treating oil-containing wastewater
• the present invention relates to an adsorbent used for the treatment of oil-containing wastewater, a method for producing the same, and a method for treating oil-containing wastewater.
• Industrial wastewater and domestic wastewater often contain oils! For example, oil refined wastewater is also discharged at various refineries.
• wastewater containing fats and oils is discharged from vegetable oil production plants as soybean oil, rapeseed oil, corn oil, etc. are produced.
• water-soluble cutting oil (mineral oil) is used for cooling and lubrication of the cutting surface in manufacturing factories that use many machine tools such as automobile factories, and wastewater containing this water-soluble mineral oil is used.
• the manufacturing plant power may be discharged.
• relatively high concentrations of oil-containing wastewater derived from animal and vegetable oils are discharged from food factories, hotels and restaurants. Therefore, when these oil-containing wastewater is treated, it is necessary to remove drainage oil.
• Oil-containing drainage power As a method for removing oil, there is a conventional method of adsorbing and removing oil using an adsorbent, and porous materials such as activated carbon and activated coatus are known as the adsorbent (for example, see Patent Document 1).
• Patent Document 1 Japanese Patent Laid-Open No. 2002-254072
• activated carbon and activated coatus used in conventional wastewater treatment are not necessarily sufficient as adsorbents for removing oil from oil-containing wastewater. That is, in the case of activated carbon and activated coatus, even if the adsorption capacity for the oil itself is relatively good, if the oil-containing wastewater is emulsion or if the oil content in the oil-containing wastewater is low, the oil content from the wastewater is sufficient. It cannot be removed.
• activated carbon and activated coatus tend to have a reduced ability to adsorb oil in a relatively short time, and there is room for improvement in terms of life.
• the present invention has been made in view of such circumstances, and even when the oil-containing wastewater is emulsion or when the oil content in the oil-containing wastewater is low, the oil content in the wastewater is reduced. It is an object of the present invention to provide an adsorbent that exhibits a sufficient adsorbing capacity and that can stably maintain the adsorbing capacity over a long period of time and a method for producing the adsorbent. Another object of the present invention is to provide an oil-containing wastewater treatment method that can stably remove oil in wastewater over a long period of time.
• the surface of activated carbon and activated coatus is often accompanied by the activation treatment, which is generally a method of activation of coal and wood with steam at 800 to 900 ° C.
• the polar groups (carboxyl group, phenolic hydroxyl group, quinone carbonyl group, etc.) formed on the surface are also considered to be the cause of the decrease in adsorption capacity for oil.
• the polar group described above is formed near the inlet of the pore because the reactivity of the surface of the carbonaceous material is higher at the edge portion than at the base portion. If present in the vicinity of the inlet, water molecules are considered to be firmly bonded to the polar group and hinder the introduction of oil into the pores.
• the present inventors examined a technique for improving the adsorption capacity for oil by improving the surface characteristics of the carbonaceous material as an approach different from the increase of the surface area due to the formation of pores. As a result, it is possible to obtain an adsorbent exhibiting an excellent adsorbing ability for oil by calcining a predetermined carbonaceous material under a specific temperature condition so that its BET surface area falls within a specific range. As a result, the present invention has been completed.
• the adsorbent of the present invention is an adsorbent for removing oil-containing drainage oil, and is obtained by calcining a predetermined carbonaceous material at 1000 to 1500 ° C. To do.
• the method for producing an adsorbent of the present invention is a method for producing an adsorbent for removing oil from an oil-containing drainage force, wherein a predetermined carbonaceous material is calcined at 1000 to 1500 ° C. It is characterized by having a baking process.
• the oil content is removed from the oil-containing wastewater by bringing the adsorbent of the present invention into contact with the oil-containing wastewater and adsorbing the oil content in the oil-containing wastewater to the adsorbent. It is characterized by.
• calcination is a force that is generally a drying process for removing volatile components and moisture contained in a carbonaceous material such as raw coatus. It is considered that most of the polar groups on the surface of the carbonaceous material are removed by calcination at 0 to 1500 ° C. The trace amount of polar groups remaining on the surface of the carbonaceous material after calcination imparts sufficient hydrophobicity (lipophilicity) to the surface, making it easy to desorb water and adsorb oil. The present inventors infer that the gender balance is realized.
• the adsorbent of the present invention preferably has a BET surface area of 20 m 2 Zg or less obtained by calcining coal-based, petroleum-based or charcoal-based coatas at 1000 to 1500 ° C. It is characterized by that.
• the oil-absorbing wastewater has sufficient adsorption capacity for the oil content in the wastewater, and the adsorption capacity thereof. It is possible to provide an adsorbent that can be stably maintained over a long period of time and a method for producing the same. Furthermore, according to the present invention, it is possible to provide a method for treating oil-containing wastewater that can stably remove oil in wastewater over a long period of time.
• FIG. 1 shows the correlation between the amount of oil-containing drainage water flow and the concentration of oil to be treated obtained in the oil adsorption capacity evaluation test for the adsorbents of Example 1 and Comparative Examples 1 and 2. It is a graph. BEST MODE FOR CARRYING OUT THE INVENTION
• the adsorbent of the present invention is obtained by calcining a predetermined carbonaceous material at 1000 to 1500 ° C.
• the carbonaceous material used as a raw material for the adsorbent is not particularly limited, but the resultant adsorbent also has the point of imparting surface characteristics that it can easily desorb water and adsorb oil. It is particularly preferred to use a coke that is preferred to use a non-porous material such as (including expanded graphite).
• a porous material such as activated coatas and activated carbon may be used as the carbonaceous material.
• these porous materials may be polar groups (carboxyl groups) formed by activation treatment. , Phenolic hydroxyl group, quinone carbonyl group, etc.) and its surface is inherently highly hydrophilic. For this reason, even if the active coatas and activated carbon are calcined at 1000 to 1500 ° C, the coatus is used more easily than in the case where the coatus is used. There is a risk that sufficient hydrophobicity (lipophilicity) cannot be imparted. Furthermore, since the adsorptive capacity of the adsorbent of the present invention is derived from its surface characteristics, the active coatas and activated carbons obtained through the activation treatment for forming a specific internal structure (pore structure) Will become expensive.
• the coatas preferably used in the present invention are not particularly limited, and heavy oil such as atmospheric residual oil, reduced pressure residual oil, tar sand, bitumen, shale oil, fluid contact cracker residual oil, coal tar, Examples include coal-based or petroleum-based coatas obtained using coal tar pitch as a raw material, or charcoal-based coatas obtained using wood, sawdust, coconut, etc. as raw materials. These raw materials may be used singly or in combination of two or more.
• the caulking process for producing the coatus is not particularly limited, and a fluid coking process, a flexi coking process, a delayed coking process, etc. can be applied.
• the heat treatment temperature in the caulking process is usually 400 to 600 ° C.
• a delayed coking process is performed. Obtained through the process-one dollar coat is preferably used.
• the carbonaceous material is calcined at 1000 to 1500 ° C to obtain the adsorbent of the present invention.
• the calcination process can be carried out using a horizontal calcination apparatus such as a rotary kiln, or a vertical calcination apparatus such as a lead hammer furnace or rotary hearth (rotary hearth calsiner).
• the treatment temperature at the time of calcination is 1000 to 1500 ° C, preferably 1200 to 1450 ° C, more preferably 1300 to 1400 ° C.
• the treatment temperature is less than 1000 ° C.
• the removal of polar groups in the surface force of the carbonaceous material becomes insufficient, and sufficient hydrophobicity cannot be imparted to the surface of the resulting adsorbent.
• the treatment temperature exceeds 1500 ° C, polar groups such as the surface of the carbonaceous material tend to be excessively removed. In this case as well, water is easily desorbed on the surface of the resulting adsorbent and the oil content is reduced. It is difficult to achieve a hydrophilic / hydrophobic balance.
• the atmosphere during calcination is not particularly limited as long as polar groups can be removed from the surface of the carbonaceous material.
• the calcination step according to the present invention is performed in the air or in nitrogen. It is preferable to carry out in an inert gas atmosphere. When calcination in the air, it is preferable to control so that the oxygen concentration in the furnace does not become excessive.
• the rate of temperature increase when the temperature is raised to the treatment temperature is 180 to 220 ° C Zh.
• the temperature near the outlet of the calcining apparatus is set to 500 to prevent acidification of the calcined coatus and suppress the formation of polar groups. It is preferable that the temperature is not higher than ° C. It is more preferable that the temperature is not higher than 300 ° C.
• the cooling method is not particularly limited, and natural cooling may be performed by leaving it alone. However, forced cooling by water cooling is preferable from the viewpoint of further improving the processing efficiency.
• the BET surface area of the obtained calcined coatus is usually 20 m 2 Zg or less, preferably 1 ⁇ : L0m 2 / g.
• the calcined coatus that is useful in the present invention has a smaller surface area than conventional activated carbon and activated coatus.
• such an adsorbent composed of calcined coatus is less than the oil content in the oil-containing wastewater.
• it shows higher adsorption capacity than conventional activated carbon and activated coatus.
• the adsorptive capacity of the adsorbent of the present invention is due to the characteristics of the surface modified by calcination.
• the particle shape is not particularly limited, but is preferably a needle shape. Further, the average particle size of the calcined coatus is preferably 0.4 to 5 mm, more preferably 1 to 2 mm.
• the adsorbent of the present invention obtained in this way, even when the oil-containing wastewater is emulsion or when the oil content in the oil-containing wastewater is low, sufficient adsorption to the oil content in the wastewater is achieved. Can be obtained, and the adsorption ability can be stably maintained over a long period of time.
• the method for treating oil-containing wastewater of the present invention is to remove the oil from the oil-containing wastewater by bringing the adsorbent of the present invention into contact with the oil-containing wastewater and adsorbing the oil in the oil-containing wastewater to the adsorbent. .
• the oil-containing wastewater to which the treatment method is applied is not particularly limited.
• Wastewater containing discharged oil and fat, wastewater containing water-soluble cutting oil (mineral oil) discharged at manufacturing plants that use machine tools, food plants and hotels and plants and animals transferred down from restaurants Examples include wastewater containing oil.
• These oil-containing wastewaters may be emulsion.
• the method of bringing the adsorbent of the present invention into contact with oil-containing wastewater is not particularly limited.
• a treatment tank similar to the activated carbon adsorption tank used for conventional wastewater treatment is filled with the adsorbent of the present invention.
• a method of passing oil-containing wastewater into the treatment tank is mentioned.
• the processing conditions such as the adsorbent filling amount, water flow rate, and processing temperature are the same as the adsorbent adsorbing capacity and the wastewater content. It can be appropriately selected in consideration of the amount of oil.
• the water flow may be either a downward flow or an upward flow, but the downward flow is preferable because the adsorbent can be easily regenerated by backwashing (upflow).
• the bag body having oil permeability for example, a sheet material made of a non-woven paper having a large number of pores formed into a bag shape having an opening can be used. After the bag is filled with the adsorbent of the invention, the opening is closed so that the adsorbent does not exert a force on the bag.
• the shape of the bag body is not particularly limited, and may be a mat shape or a rod shape.
• the bag filled with the adsorbent of the present invention can be used in the case of treating oil-containing wastewater from the above-described refineries, factories, etc. It is useful for pollution prevention treatment and waste oil treatment at home.
• the needle coat (S JA calcined powder coat) is heated to 1300 ° C at a heating rate of about 3-4 ° CZ. Calcinated at 0 ° C for 4 hours. Thereafter, forced cooling by water cooling was performed, and the calciner outlet temperature was maintained at 120 ° C. to obtain a calcined coatus having a BET surface area of 3 m 2 / g.
• a calcined coat with a BET surface area of 3m 2 Zg was obtained in the same manner as in Example 1 except that the treatment temperature when calcining the needle coat was 1000 ° C. Provided.
• the one-dollar coat (BET surface area 3 m 2 Zg) used as a raw material in Example 1 was subjected to the following test as an adsorbent of Comparative Example 2 without being calcined.
• Activated carbon (trade name: Dazai activated carbon GM130A, manufactured by Nimura Chemical Co., Ltd., BET surface area: 1000 m 2 / g) was subjected to the following test as an adsorbent of Comparative Example 3.
• Example 2 The following tests were performed on the adsorbents of Example 2 and Comparative Example 1 to evaluate the adsorbing ability for oil in the oil-containing wastewater.
• the adsorbent lOOmL was packed in a column (capacity: 150 mL). Wastewater containing a predetermined concentration of oil was passed through the column at a water flow rate of 150 mLZ, and the oil concentration of the treated water that passed through the column was measured.
• Table 1 shows the flow rate and oil content of oil-containing wastewater, and the oil content of treated water. [0047] [Table 1]
• Example 1 The following tests were performed on the adsorbents of Example 1 and Comparative Examples 2 and 3, and the adsorbing ability for oil in the oil-containing wastewater was evaluated.
• 30 mL of the adsorbent was packed in a column (volume: lOOmL).
• the oil-containing wastewater having an oil concentration of 50 mg / L was passed through this column at a water flow rate of 60 mL / min, and the oil concentration of the treated water that passed through the column was measured.
• Figure 1 shows the correlation between the amount of oil-containing wastewater flow and the concentration of treated water.
• the adsorbents lOOmL of Examples 1 and 2 and Comparative Examples 1 to 3 were placed in a separatory funnel together with AOO oil A lOOmL and stirred, and allowed to stand for 2 days. Subsequently, A heavy oil was dropped and separated, and the lipophilicity of each adsorbent was evaluated based on the recovered amount of A heavy oil. Table 2 shows the results obtained.
• the adsorbent of Example 2 has a smaller surface area compared to the adsorbent of Comparative Example 3 using activated carbon, and the adsorption capacity in the case of A heavy oil alone is low. Regardless, it showed a high adsorption capacity for the oil in the oil-containing wastewater.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Analytical Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Hydrology & Water Resources (AREA)
• Thermal Sciences (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Environmental & Geological Engineering (AREA)
• Water Supply & Treatment (AREA)
• Water Treatment By Sorption (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Sewage (AREA)
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• Carbon And Carbon Compounds (AREA)

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• 2004
  • 2004-09-17 JP JP2004272357A patent/JP4444051B2/ja not_active Expired - Lifetime
• 2005
  • 2005-09-06 US US11/662,942 patent/US7666306B2/en not_active Expired - Lifetime
  • 2005-09-06 WO PCT/JP2005/016317 patent/WO2006030668A1/ja not_active Ceased
  • 2005-09-06 EP EP05782199A patent/EP1806321A4/en not_active Withdrawn
  • 2005-09-06 CN CNA2005800311866A patent/CN101039879A/zh active Pending

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