WO2019163062A1 - Adsorbant et son procédé de préparation - Google Patents

Adsorbant et son procédé de préparation Download PDF

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Publication number
WO2019163062A1
WO2019163062A1 PCT/JP2018/006541 JP2018006541W WO2019163062A1 WO 2019163062 A1 WO2019163062 A1 WO 2019163062A1 JP 2018006541 W JP2018006541 W JP 2018006541W WO 2019163062 A1 WO2019163062 A1 WO 2019163062A1
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WO
WIPO (PCT)
Prior art keywords
adsorbent
thermoplastic resin
reverse osmosis
osmosis membrane
winding
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PCT/JP2018/006541
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English (en)
Japanese (ja)
Inventor
哲郎 上山
優紀 川原
板山　朋聡
秀二 田邉
裕人 村上
Original Assignee
協和機電工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 協和機電工業株式会社 filed Critical 協和機電工業株式会社
Priority to PCT/JP2018/006541 priority Critical patent/WO2019163062A1/fr
Priority to JP2018534178A priority patent/JP6439084B1/ja
Priority to JP2020501607A priority patent/JP6831157B2/ja
Priority to PCT/JP2019/002463 priority patent/WO2019163400A1/fr
Publication of WO2019163062A1 publication Critical patent/WO2019163062A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
    • B01D29/11—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor with bag, cage, hose, tube, sleeve or like filtering elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/007—Addition polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/009—Condensation or reaction polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/016—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the fineness
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion

Definitions

  • the present invention relates to an adsorbent and a method for producing the adsorbent. Specifically, by selectively adsorbing specific suspended substances and soluble substances that cause the membrane blockage of the reverse osmosis membrane, the membrane blockage of the reverse osmosis membrane can be prevented in advance, and the lifetime of the reverse osmosis membrane
  • the present invention relates to an adsorbent and a method for manufacturing the adsorbent that can reduce the running cost of the entire water treatment apparatus.
  • Patent Document 1 For example, in Patent Document 1, first, an organic substance contained in water to be treated is biologically treated, followed by aggregation and solid-liquid separation treatment, and solid-liquid separation treatment water is suspended by membrane filtration treatment.
  • a water treatment system is disclosed in which pure water is generated through a process of treating water to be treated in a wastewater recycling facility equipped with a reverse osmosis membrane (RO membrane) after removing turbid substances and the like.
  • RO membrane reverse osmosis membrane
  • the reverse osmosis membrane method using a reverse osmosis membrane is a method of obtaining pure water in which treated water is purified by treating salt water with a reverse osmosis membrane at a high pressure.
  • desalted water can be produced by applying a pressure equal to or higher than the osmotic pressure to the water to be treated containing salt such as seawater, brine, or wastewater, and allowing the reverse osmosis membrane to permeate.
  • the reverse osmosis membrane used in reverse osmosis treatment may clog the membrane (fouling), and the amount of filtered water for the treated water may decrease. is there.
  • the causative substances of this membrane clogging are metal and organic matter derived from wastewater, polymeric organic matter generated by biological treatment in the previous stage, metal-based flocculant injected in the previous stage aggregation and solid-liquid separation processing, and metal derived therefrom and polymer aggregation. A part of the agent is included.
  • a reverse osmosis membrane made of a polyamide-based material in particular has a high desalting rate and excellent organic matter removal properties, but is prone to organic contamination, so the permeation flow rate tends to decrease. There is. For this reason, before supplying to the reverse osmosis membrane, a method of adsorbing and removing contaminants of the water to be treated using an adsorbent such as activated carbon is sometimes used. Since it is adsorbed by the adsorbent, there is a problem that the amount of adsorbent used increases and the cost increases.
  • an adsorbent filled with an adsorbent made of activated carbon or zeolite as a raw material is used as a pretreatment for a reverse osmosis membrane in order to remove organic substances contained in seawater or brine.
  • a reverse osmosis membrane By installing it before the reverse osmosis membrane, the concentration of organic substances reaching the reverse osmosis membrane is reduced by the adsorption reaction by the adsorbent and intake by microorganisms grown on the surface of the adsorbent, thereby reducing the membrane blockage of the reverse osmosis membrane Techniques to do this have been proposed.
  • Patent Document 2 discloses a water treatment system in which two reverse osmosis membranes are connected in series. Specifically, a first reverse osmosis membrane is provided in the front stage, a second reverse osmosis membrane is provided in the rear stage, and the concentrated water that has not permeated through the first reverse osmosis membrane is filtered through the second reverse osmosis membrane. It is possible to disperse the burden on the reverse osmosis membrane, prevent deterioration of the reverse osmosis membrane as a whole, and extend the useful life of the reverse osmosis membrane.
  • Patent Document 3 discloses a water treatment apparatus provided with an adsorbing means using an adsorbent containing a powdery substance obtained by pulverizing a polyamide resin close to a material constituting a reverse osmosis membrane. According to Patent Document 3, since the adsorbent is made of the same polyamide resin as the constituent material of the reverse osmosis membrane, a substance that is easily adsorbed on the reverse osmosis membrane is selectively adsorbed in the adsorbent that is the previous stage. Thus, it is possible to prevent the reverse osmosis membrane from being deteriorated and reduce the amount of the adsorbent used.
  • JP 2008-73622 A Japanese Patent Laid-Open No. 11-47566 JP 2003-275760 A
  • the second reverse osmosis membrane filters concentrated water in which impurities are concentrated, so that the operation burden is large. Therefore, there is a problem that the second reverse osmosis membrane is deteriorated faster than the first reverse osmosis membrane, so that the service life is shortened and the quality of the permeated water obtained is also lowered.
  • the adsorbent uses a pulverized polyamide resin, but the total surface area is not necessarily large, and the amount of the suspended matter to be adsorbed is also adsorbed. It will be limited. For this reason, it is necessary to frequently replace the adsorbent, and the running cost is high, which is not necessarily practical. Furthermore, since powder is used, it is difficult to realize the shape of the product for applying the powder to actual equipment, and the water loss energy becomes too high due to the large pressure loss when water is passed through the powder. There was a problem.
  • the present invention was devised in view of the above points, and by selectively adsorbing a specific suspended substance or soluble substance that causes the blockage of the reverse osmosis membrane, the reverse osmosis membrane
  • An object of the present invention is to provide an adsorbent capable of preventing membrane clogging and extending the service life of a reverse osmosis membrane and reducing the running cost of the entire water treatment apparatus, and a method for producing the adsorbent.
  • the adsorbent of the present invention comprises a laminate in which a thermoplastic resin having an average diameter of approximately 0.5 to 10 ⁇ m is laminated, and the packing density of the laminate is approximately 0.20 to 0.40 g / mL and a specific surface area of about 0.33 to 6.54 m 2 / g.
  • thermoplastic resin as the material constituting the adsorbent, it is possible to easily produce fine fibers at a low cost, and also has excellent durability and specific suspended substances and solubility. Substances can be selectively adsorbed.
  • the average diameter of the thermoplastic resin is approximately 0.5 to 10 ⁇ m
  • the packing density of the laminate in which the thermoplastic resin is laminated is approximately 0.20 to 0.40 g / mL
  • the specific surface area is 0.33 to 6 Since the adsorption capacity of the adsorbent can be increased by being .54 m 2 / g, a specific suspended substance or soluble substance can be selectively adsorbed in a large amount. For this reason, it is possible to prevent the reverse osmosis membrane installed at the subsequent stage of the adsorbent from deteriorating and maintain the adsorption performance of the reverse osmosis membrane for a long period of time.
  • the fibers having a small average diameter are laminated, a space between the fibers is appropriately secured, and water permeation due to capillary action also occurs, so that the water flow resistance of the adsorbent can be lowered. Therefore, the water to be treated can be passed through the adsorbent with a small applied pressure. Therefore, the running cost of the whole water treatment apparatus in which the adsorbent is installed can be suppressed.
  • the diameter of the fiber constituting the adsorbent is increased, so that the specific surface area of the adsorbent is reduced, so that the adsorption capacity of suspended substances and soluble substances is limited. End up. Therefore, it is necessary to change the adsorbent frequently. Further, since the adsorption reaction time is shortened by reducing the surface area, the treatment performance is reduced, the deterioration of the reverse osmosis membrane installed at the subsequent stage of the adsorbent is accelerated, and the replacement cycle of the reverse osmosis membrane is shortened. For this reason, there exists a possibility that the running cost of the whole water treatment apparatus may rise.
  • the average diameter is less than 0.5 ⁇ m
  • there is a manufacturing limit in the melt-blowing method which is a relatively inexpensive manufacturing method.
  • the packing density is less than 0.20 g / mL
  • the adsorption capacity of suspended substances and soluble substances by the adsorbent is limited. Therefore, the deterioration of the reverse osmosis membrane installed in the subsequent stage of the adsorbent is accelerated, and the replacement cycle of the reverse osmosis membrane is shortened.
  • gap between fibers becomes large too much, the intensity
  • melt-blowing method which is a relatively inexpensive manufacturing method, has a manufacturing limit. For example, it is necessary to use an electrospinning method, which may increase the manufacturing cost.
  • the specific surface area is less than 0.33 m 2 / g
  • the adsorption capacity of the suspended substance and the soluble substance by the adsorbent is limited. Therefore, the deterioration of the reverse osmosis membrane installed in the subsequent stage of the adsorbent is accelerated, and the replacement cycle of the reverse osmosis membrane is shortened.
  • the adsorption capacity per unit mass of the adsorbent decreases, it is necessary to increase the size of the adsorbent in order to ensure a constant amount of adsorption. There is a possibility that the cost increases and the running cost of the entire water treatment apparatus increases.
  • the thermoplastic resin is a semi-aromatic polyamide resin
  • the semi-aromatic polyamide resin is a material having a benzene ring, so that the adsorption performance of a specific suspended substance or soluble substance can be improved.
  • an adsorbent is installed upstream of a reverse osmosis membrane with a high proportion of benzene rings as a constituent material, suspended substances and soluble substances adsorbed on the reverse osmosis membrane must be adsorbed in advance by the adsorbent. Therefore, deterioration of the reverse osmosis membrane can be prevented, and the adsorption performance of the reverse osmosis membrane can be maintained for a long period of time.
  • thermoplastic resin is an MXD resin
  • MXD resin it is easy to adjust the filling density, and therefore, an adsorbent having a high filling density can be produced. Therefore, it is possible to selectively adsorb a large amount of suspended substances and soluble substances on the adsorbent.
  • the method for producing an adsorbent according to the present invention comprises injecting a molten thermoplastic resin by an air flow so that the average diameter is approximately 0.5 to 10 ⁇ m. And a step of winding the thermoplastic resin fiberized by the melt blowing step under a temperature condition equal to or higher than the glass transition point of the thermoplastic resin.
  • a step of injecting the molten thermoplastic resin by an air flow and melt-blowing the thermoplastic resin to have an average diameter of about 0.5 to 10 ⁇ m is provided. It can be.
  • the diameter of the fibers constituting the adsorbent becomes large, which lowers the packing density of the adsorbent and reduces the specific surface area.
  • the adsorption capacity is limited. Therefore, it is necessary to change the adsorbent frequently.
  • the adsorption reaction time is shortened by reducing the surface area, the processing performance is reduced and the reverse osmosis membrane installed downstream of the adsorbent is deteriorated in a short time, and the reverse osmosis membrane replacement cycle is short. Become. For this reason, there exists a possibility that the running cost of the whole water treatment apparatus may rise.
  • the melt blow method which is a relatively inexpensive production method, has production limitations, and for example, it is necessary to use an electrospinning method, which may increase the production cost. There is.
  • the crystallization of the thermoplastic resin is advanced at a constant speed simultaneously with the winding. be able to.
  • the injected average diameter can be made into a fine fiber shape of about 0.5 to 10 ⁇ m.
  • An adsorbent having a high packing density and a large specific surface area can be produced.
  • thermoplastic resin cannot be made into fine fibers, such as an average diameter of 0.5 to 10 ⁇ m, and the specific surface area is reduced, so that the adsorbent suspended or soluble substances The adsorption capacity is limited.
  • the melting temperature is less than 250 ° C.
  • the thermoplastic resin is insufficiently melted and the average diameter cannot be made into a fine fiber shape of about 0.5 to 10 ⁇ m. Therefore, since the total surface area is also reduced, the adsorption capacity of suspended substances and soluble substances in the adsorbent is limited.
  • the step of melt-blowing the thermoplastic resin involves winding the thermoplastic resin, which will be described later, when the thermoplastic resin is injected with an air flow having a temperature of about 300 to 500 ° C. and a flow rate of about 150 to 300 m / sec.
  • the thermoplastic resin can be wound up and at the same time, the thermoplastic resin can be gradually crystallized and contracted, so that an adsorbent having a high packing density, a large total surface area, and a low water resistance is manufactured. be able to.
  • thermoplastic resin cannot be made into fine fibers such as an average diameter of 0.5 to 10 ⁇ m, so that the specific surface area is reduced and the suspended substance or soluble substance of the adsorbent is reduced. Adsorption capacity is limited.
  • the temperature of the air flow at the time of melt blowing is less than 300 ° C.
  • the melted heat-sparing resin is cooled before being formed into a fiber by melt blowing, so that the average diameter is as small as 0.5 to 10 ⁇ m. It becomes difficult to make it fibrous.
  • the flow velocity of the air flow at the time of melt blowing is higher than 300 m / sec, the injected thermoplastic resin is cut before being drawn into fine fibers, and the average diameter is set to 0.5 to 10 ⁇ m. Therefore, the adsorption capacity of the suspended substance and the soluble substance of the adsorbent is limited.
  • the flow rate of the air flow at the time of melt blowing is less than 150 m / sec, the average diameter of the thermoplastic resin fiberized by injection cannot be made into a fine fiber shape of about 0.5 to 10 ⁇ m. For this reason, the packing density of the adsorbent cannot be increased, and the total surface area is also reduced, so that the adsorption capacity of the suspended substance or soluble substance of the adsorbent is limited.
  • the step of winding the thermoplastic resin is constant after a predetermined time has elapsed after winding when the surface temperature of the thermoplastic resin during winding is approximately 100 to 150 ° C.
  • the crystallization of the thermoplastic resin can proceed at a rate of Thereby, without melting the laminated body laminated by winding the fiber, it is possible to gradually advance the crystallization after winding, because the entire laminated body shrinks in the radial direction and the length direction, An adsorbent having a high packing density, a large total surface area, and a low water resistance can be produced.
  • thermoplastic resin at the time of winding when the surface temperature of the thermoplastic resin at the time of winding is higher than 150 ° C., the crystallization of the thermoplastic resin at the time of winding is accelerated, so that it is crystallized simultaneously with the winding. For this reason, the shrinkage of the laminate accompanying the crystallization after winding is not promoted, so that the packing density cannot be increased, and the adsorption capacity of the adsorbent suspended substance and the soluble substance is limited.
  • the surface temperature of the thermoplastic resin at the time of winding is less than 100 ° C.
  • the crystallization speed of the thermoplastic resin becomes slow, and it takes a long time for the thermoplastic resin to shrink after winding, and the shrinkage rate May fall.
  • the packing density cannot be increased, and the adsorption capacity of the suspended substance and the soluble substance of the adsorbent is limited.
  • the step of winding up the thermoplastic resin when it has a step of heating the thermoplastic resin in an oven device under a predetermined temperature condition, the crystallization of the laminated body in which the fibers are laminated is gradually advanced. Since the entire laminate contracts in the radial direction and the length direction, it is possible to produce an adsorbent with a high packing density, a large total surface area, and a low water resistance.
  • the laminate in which the fibers are laminated is heated by warm water. Crystallization can be further advanced, and the entire laminate shrinks in the radial direction and length direction, so that an adsorbent with a high packing density, a large total surface area, and a low water resistance can be produced. . Furthermore, impurities such as organic substances accumulated in the laminate can be removed by washing by passing warm water.
  • the adsorbent according to the present invention and the method for producing the adsorbent selectively occlude the membrane of the reverse osmosis membrane by selectively adsorbing a specific suspended substance or soluble substance that causes the membrane occlusion of the reverse osmosis membrane. Can be prevented, the service life of the reverse osmosis membrane can be extended, and the running cost of the entire water treatment apparatus can be reduced.
  • FIG. 1A is a perspective view
  • FIG. 2B is an XX cross-sectional view of FIG. 1A, illustrating an adsorbent according to an embodiment of the present invention. It is a figure which shows the adsorption body manufacturing apparatus for manufacturing an adsorption body in embodiment of this invention.
  • FIG.1 (a) shows the schematic of the general water treatment system 1 installed in a factory etc., for example.
  • the water treatment system 1 a part of the treated water W2 flowing out from the tap water (tap water) W1 and the wastewater recycling facility 2 passes through the pure water production apparatus 3 and is produced as high-purity water. Used for applications (product water W21, cooling water W22, washing water W23).
  • the water used in the factory flows into the wastewater treatment facility 4 as factory wastewater W3, a part thereof is discharged as sewage W4, and the remaining part flows into the wastewater recycling facility 2 as wastewater treatment water W5.
  • the wastewater treated water W5 that has flowed into the wastewater recycling facility 2 is recycled after removing suspended substances, and is used again for each application in the factory together with the clean water W1.
  • FIG. 1B is a schematic view of the wastewater recycling facility 2 described above.
  • an adsorbent 21 according to the present invention is arranged on the upstream side, and a reverse osmosis membrane 22 is arranged on the downstream side in series.
  • the reverse osmosis membrane 22 has a known structure, and specifically includes a membrane separation layer made of a polyamide material.
  • the adsorbent 21 is made of a material having a structure close to the polyamide-based material constituting the reverse osmosis membrane 22, specifically, a polyamide resin.
  • the upstream adsorbent 21 adsorbs to the polyamide-based material among the organic substances contained in the wastewater treated water W5. Suspended substances and soluble substances having the above properties are selectively adsorbed.
  • the wastewater treated water W5 that has passed through the adsorbent 21 subsequently flows into the reverse osmosis membrane 22, and further ionic substances such as salt are removed, and finally, the treated water W2 is out of the system of the wastewater recycling facility 2. To be reused for various purposes in the factory.
  • ionic substances such as salinity in the wastewater treated water W5 separated by the reverse osmosis membrane 22 are discharged out of the wastewater recycling facility 2 and processed as concentrated water W6.
  • Suspended substances and soluble substances selectively adsorbed by the adsorbent 21 are carried out of the system while adsorbed on the adsorbent 21 or used as washing wastewater by regenerating and washing the adsorbent. Is discharged out of the diameter.
  • the effluent treated water W5 flowing into the reverse osmosis membrane 22 is quantified by a suspended substance or a soluble substance that is a causative substance of the reverse osmosis membrane 22 due to the adsorbent 21 installed in the preceding stage. Has been removed. Therefore, since the amount of suspended substances and soluble substances adsorbed on the reverse osmosis membrane 22 is suppressed, membrane clogging is unlikely to occur, and the lifetime of the reverse osmosis membrane 22 can be extended.
  • the above is the overall outline of the water treatment system 1 including the wastewater recycling facility 2 to which the adsorbent 21 according to the present invention is applied.
  • the reverse osmosis membrane 22 as described above is not necessarily used as the adsorbent 21 of the present invention.
  • the present invention is not limited to the use for the purpose of removing the causative substance of the membrane clogging, but may be used for other purposes.
  • a forward osmosis membrane such as a drainage concentration / reduction process using a forward osmosis membrane, it is used to reduce the risk of membrane blockage of the forward osmosis membrane and is close to the forward osmosis membrane.
  • the adsorbent 21 of the present invention can also be used to selectively adsorb and remove trace substances contained in the water when the wastewater treated water is discharged or when water is taken in the water purification facility. Furthermore, the adsorbent 21 of the present invention can also be used when only the impurities are selectively adsorbed and removed in order to increase the purity in food production, pharmaceutical production, ink production, or the like.
  • the adsorbent 21 according to the embodiment of the present invention is manufactured by a melt blowing method, which is a known method of manufacturing a molten thermoplastic resin by drawing it with an air flow, and has become a fine fiber by melt blowing.
  • the thermoplastic resin is composed of a substantially cylindrical laminate 211 having a through hole 212 formed in the center.
  • the laminate 211 is not necessarily required to be substantially cylindrical.
  • any shape may be used as long as it has a hollow shape such as a square tube or an elliptical tube.
  • the adsorbent 21 is not necessarily manufactured by the melt blow method.
  • it can be produced by an electrospinning method.
  • the electrospinning method has a high manufacturing cost, the manufacturing method in the embodiment of the present invention will be described based on an example of a melt-blowing method that is a relatively inexpensive manufacturing method.
  • the adsorbent 21 has an outer diameter d of about 60 to 75 mm and a length l of about 125 to 1000 mm, and the fiber material constituting the laminate 211 has an average diameter of about 0.5 to 10 ⁇ m.
  • an adsorbent 21 having an outer diameter d of 70 mm and a length l of 125 mm was used as the adsorbent 21 in the embodiment of the present invention.
  • the thermoplastic resin used as the material of the fiber material is preferably a resin material capable of adjusting the crystallization speed at the time of winding, and as described above, is a polyamide resin, more preferably a semi-aromatic polyamide resin, and particularly an MXD resin.
  • nylon MXD6 resin manufactured by Mitsubishi Gas Chemical Company, “MX nylon”, grade name “S6001” is employed as the MXD resin.
  • nylon MXD6 In the embodiment of the present invention, an example in which the above-described nylon MXD6 is adopted is shown.
  • nylon 6 resin (trade name “Amilan”, grade name “CM1017” manufactured by Toray Industries, Inc.), recycled nylon 6 Resin (trade name “Tanadine”, grade name “TN200” manufactured by Takayasu Co., Ltd.), nylon 66 resin (trade name “Amilan”, grade name “CM3007” manufactured by Toray Industries, Inc.), recycled nylon 66 resin (Takayasu Co., Ltd.)
  • Product name "Tanadine", grade name "TN720” recycled nylon 6-MXD resin (manufactured by Takayasu Co., Ltd., trade name "Tanadine", grade name "6N-MXD33”)
  • polyamide resin Mitsubishi Gas Chemical Co., Ltd.
  • LEXTER grade name “8000”
  • polypropylene resin manufactured by Sun Aroma Co., Ltd., trade name “SUN ALO
  • the adsorbent manufacturing apparatus 5 mainly includes a melt injection apparatus 51, a hot air apparatus 52, and a winding apparatus 53.
  • the melt injection device 51 includes a hopper 511 for introducing a thermoplastic resin, a screw 513 that is extruded through a motor 512 while melting the thermoplastic resin introduced from the hopper 511 at a high temperature, and an injection for injecting the molten thermoplastic resin. It consists of an injection nozzle 514.
  • thermoplastic resin introduced from the hopper 511 is melted at a predetermined temperature by the heater. It is like that.
  • the injection nozzle 514 is provided with an air inlet (not shown), and the air inlet is connected to an external compressor (not shown).
  • a pressure reducing valve that controls the air pressure from the compressor
  • a flow meter that measures the air flow rate
  • a regulator that adjusts the air flow rate (for example, a needle valve) are connected between the pipes that connect the compressor to the air heating device. May be.
  • the molten thermoplastic resin is formed into fine fibers by being sprayed with high-temperature and high-speed hot air when it is injected from the injection nozzle 514.
  • the warm air device 52 blows warm air at a constant temperature against the fiberized thermoplastic resin, so that the surface temperature of the thermoplastic resin during winding by the winding device 53 described later is equal to or higher than the glass transition point.
  • This is a device for adjusting the temperature so that
  • the warm air device 52 it is not always necessary to provide the warm air device 52. Any device may be used as long as the temperature can be adjusted so that the surface temperature of the thermoplastic resin at the time of winding by the winding device 53 is equal to or higher than the glass transition point.
  • the winding device 53 includes a core bar 531 for winding up the thermoplastic resin that has been melt blown into fine fibers.
  • One end of the core bar 531 is attached to the motor 532, and the motor 532 is rotated according to the number of rotations of the motor 532. It is configured to rotate at a constant rotational speed and to reciprocate along the axial direction of the core bar 531. Note that the distance L between the core bar 531 and the injection nozzle 514 is arranged at a position approximately 15 to 20 cm apart.
  • the distance L between the core bar 531 and the injection nozzle 514 is not necessarily separated by about 15 to 20 cm.
  • the thermoplastic resin in the form of fibers is wound around the core bar 531 as described later.
  • the surface temperature at the time of taking becomes the temperature suitable for the crystallization of the thermoplastic resin, and the adsorbent 21 having a high packing density and a large specific surface area can be obtained.
  • thermoplastic resin into melt injection apparatus (S1)> First, a predetermined amount of nylon MXD6 resin is introduced into the melt injection apparatus 51 from the hopper 511 as a thermoplastic resin.
  • thermoplastic resin (S2)> Next, the charged thermoplastic resin is melted and softened by a heater under a temperature condition of approximately 250 to 330 ° C., and the softened thermoplastic resin is extruded toward the injection nozzle 514 by a screw 513.
  • the melting condition is not necessarily about 250 to 330 ° C.
  • the average diameter of the thermoplastic resin when it is fiberized is as fine as about 0.5 to 10 ⁇ m by melting under a temperature condition of about 250 to 330 ° C.
  • the adsorbent 21 having a high packing density and a large specific surface area was obtained for the laminated body 211 after winding.
  • thermoplastic resin softened by melting is injected together with high-temperature and high-speed hot air from the injection nozzle 514 toward the core bar 531 of the winding device 53.
  • the temperature of hot air is set to about 300 to 500 ° C.
  • the flow rate is set to about 150 to 300 m / sec.
  • the hot air temperature is about 300 to 500 ° C. and the flow rate is 150 to 300 m / sec.
  • the average diameter of the thermoplastic resin when melt blown is about 0.5 by setting the hot air temperature to about 300 to 500 ° C. and the flow rate to 150 to 300 m / sec. It was able to be set to ⁇ 10 ⁇ m.
  • thermoplastic resin that has become fine fibers is wound around a core rod 531 that rotates at a constant rotational speed (approximately 45 rpm) and reciprocates at a constant reciprocating speed (approximately 4 to 25 mm / sec).
  • a fiber laminate 211 having a length and a thickness is formed.
  • the temperature adjustment is performed by the warm air device 52 so that the surface temperature of the thermoplastic resin when being wound by the winding device 53 is approximately 120 to 150 ° C.
  • the rotational speed of the core bar 531 is not necessarily about 45 rpm, and the reciprocating speed is not necessarily about 4 to 25 mm / sec.
  • the surface temperature of the thermoplastic resin at the time of winding is set to a range of 120 to 150 ° C. by using the rotation speed, the forward movement, and the reciprocating speed.
  • shrinkage can be achieved by proceeding with crystallization of the laminate, and an adsorbent with a high packing density can be produced.
  • the core bar 531 does not necessarily need to be reciprocated in the axial direction.
  • the stacked body 211 can be configured without reciprocating the core bar 531.
  • step (S7) of cleaning the adsorbent 21 it is not always necessary to perform the step (S7) of cleaning the adsorbent 21.
  • this step need not be performed.
  • the laminated body 211 constituting the adsorbent body 21 is not sufficiently contracted by passing warm water having a constant temperature through the adsorbent body 21, the laminated body 211 is further contracted by the heating effect of the hot water. Therefore, the packing density of the entire adsorbent 21 can be increased.
  • the surface temperature of the thermoplastic resin at the time of winding is equal to or higher than the glass transition point of nylon MXD6 and is in a temperature range where crystallization is moderately promoted.
  • a condition is set.
  • crystallization of the fine fibrous thermoplastic resin constituting the laminated body 211 can be delayed in the winding stage, and therefore the laminated body 211 that forms the three-dimensional network structure is provided. Can be obtained.
  • the laminated body 211 having a three-dimensional network structure is gradually crystallized, so that the entire laminated body 211 contracts in the radial direction and the length direction.
  • the packing density of the laminate 211 is increased, so that an adsorbent having a large specific surface area and a low water resistance can be manufactured.
  • the adsorbent 21 manufactured by the above manufacturing method will be described based on Table 1 below.
  • nylon MXD6 is used as the thermoplastic resin, and the adsorbent 21 has a diameter of 70 mm and a length of 125 mm. Used and compared.
  • Example 1 The production conditions in the adsorbent production apparatus 5 were set so that the average diameter was 0.52 ⁇ m, and the surface temperature during winding was 135 ° C., the packing density was 0.34 g / mL, and the specific surface area was 6.30 m 2 / g of adsorbent 21 was obtained.
  • Example 2 The production conditions in the adsorbent production apparatus 5 were set so that the average diameter was 2.44 ⁇ m and the surface temperature during winding was 120 ° C., the packing density was 0.29 g / mL, and the specific surface area was 1.34 m 2 / g of adsorbent 21 was obtained.
  • Example 3 The production conditions in the adsorbent production apparatus 5 were set so that the average diameter was 3.82 ⁇ m and the surface temperature during winding was 115 ° C., the packing density was 0.26 g / mL, and the specific surface area was 0.817 m 2 / g of adsorbent 21 was obtained.
  • Example 4 The production conditions in the adsorbent production apparatus 5 are set so that the average diameter is 7.01 ⁇ m and the surface temperature during winding is 115 ° C., the packing density is 0.21 g / mL, and the specific surface area is 0.471 m 2 / g of adsorbent 21 was obtained.
  • Example 5 The production conditions in the adsorbent production apparatus 5 were set so that the average diameter was 9.98 ⁇ m, and the surface temperature during winding was 115 ° C., the packing density was 0.28 g / mL, and the specific surface area was 0.327 m 2 / g of adsorbent 21 was obtained.
  • the adsorbents 21 of Examples 1 to 5 have higher adsorbability of suspended substances and soluble substances than the adsorbents 21 of Comparative Examples 1 to 4. . That is, in Examples 1 to 5, the average diameter is 0.5 to 10 ⁇ m, the surface temperature of the thermoplastic resin during winding is equal to or higher than the glass transition point of nylon MXD6, and the crystallization is moderate. Conditions in each manufacturing process are set so as to be a temperature region that advances. In the winding stage, crystallization of the fine fibrous thermoplastic resin constituting the laminate 211 can be delayed, so that the laminate 211 forming a three-dimensional network structure can be obtained.
  • the laminated body 211 having a three-dimensional network structure gradually crystallizes, so that the entire laminated body 211 contracts in the radial direction and the length direction. Accordingly, since the packing density of the stacked body 211 is increased, the adsorbent 21 having a large specific surface area and a high adsorbing ability can be manufactured.
  • the adsorbent according to the present invention and the method for producing an adsorbent selectively adsorb a specific suspended substance or soluble substance that causes the membrane clogging of the reverse osmosis membrane.
  • Membrane blockage can be prevented in advance, the service life of the reverse osmosis membrane can be extended, and the running cost of the entire water treatment apparatus can be reduced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
  • Removal Of Floating Material (AREA)
  • Nonwoven Fabrics (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème décrit par la présente invention est de fournir : un adsorbant qui peut réduire le coût de fonctionnement total d'un appareil de traitement d'eau tout en empêchant une obstruction de membrane dans une membrane d'osmose inverse à l'avance et l'extension de la durée de vie utile de la membrane d'osmose inverse par adsorption sélective de matériaux en suspension spécifiques ou de matériaux solubles qui provoquent une obstruction de membrane dans la membrane d'osmose inverse; et un procédé de préparation de l'adsorbant. La solution selon l'invention porte sur un adsorbant 21 qui comprend de préférence un stratifié dans lequel, parmi des résines thermoplastiques ayant un diamètre moyen d'environ 0,5 à 10 µm, des résines de nylon MXD6 sont stratifiées, ledit stratifié ayant une densité de tassement d'environ 0,20 à 0,40 g/mL et une surface spécifique d'environ 0,33-6,54 m2/g.
PCT/JP2018/006541 2018-02-22 2018-02-22 Adsorbant et son procédé de préparation WO2019163062A1 (fr)

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PCT/JP2018/006541 WO2019163062A1 (fr) 2018-02-22 2018-02-22 Adsorbant et son procédé de préparation
JP2018534178A JP6439084B1 (ja) 2018-02-22 2018-02-22 吸着体、および吸着体の製造方法
JP2020501607A JP6831157B2 (ja) 2018-02-22 2019-01-25 油吸着体の製造方法
PCT/JP2019/002463 WO2019163400A1 (fr) 2018-02-22 2019-01-25 Adsorbant d'huile et procédé de production d'adsorbant d'huile

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WO2019163400A1 (fr) 2019-08-29

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