Porous molding

Abstract

Provided is a porous molding which is capable of removing ions in water to be treated, in particular, phosphorus ions at a very high liquid-permeation rate of at least SV 120 hr.sup.1, and which has a large adsorption capacity. The porous molding according to the present invention comprises an organic polymer resin and an inorganic ion adsorbent, and is characterized in that a total volume of pores having a pore diameter of 1-80 nm as measured by a nitrogen adsorption method is 0.05-0.7 cm.sup.3/g per unit mass of the inorganic ion adsorbent.

Claims

1. A porous shaped body in which an organic polymer resin and an inorganic ion adsorbent are included, and the sum total of the volumes of pores having a pore diameter of from 1 nm to 80 nm measured by a nitrogen gas adsorption method is per unit mass of the inorganic ion adsorbent from 0.05 cm.sup.3/g to 0.7 cm.sup.3/g wherein the elastic modulus of the porous shaped body is from 1000 mN/m.sup.2 to 12000 mN/m.sup.2.

2. The porous shaped body according to claim 1, wherein the sum total of the volumes of pores having a pore diameter of from 1 nm to 80 nm measured by a nitrogen gas adsorption method is per unit mass of the porous shaped body from 0.02 cm.sup.3/g to 0.6 cm.sup.3/g.

3. The porous shaped body according to claim 1, wherein the specific surface area measured by a nitrogen gas adsorption method is from 50 m.sup.2/g to 400 m.sup.2/g.

4. The porous shaped body according to claim 1, wherein the supported amount of the inorganic ion adsorbent included in the porous shaped body is from 30% by mass to 95% by mass.

5. The porous shaped body according to claim 1 in a form of spherical particles with an average particle diameter of from 100 m to 2500 m.

6. The porous shaped body according to claim 1, wherein the flatness ratio of the porous shaped body particles is from 0 to 0.3.

7. The porous shaped body according to claim 1, wherein the bulk density of the porous shaped body is from 0.2 g/mL to 0.7 g/mL.

8. The porous shaped body according to claim 1, wherein the average particle diameter of an inorganic ion adsorbent included in the porous shaped body is from 0.08 m to 10 m, and the ratio of (maximum particle diameter)/(minimum particle diameter) of the inorganic ion adsorbent is from 1 to 500.

9. The porous shaped body according to claim 1, wherein the pore volume measured by a mercury intrusion method in a range of pore diameter of from 5.5 nm to 120 m is from 0.6 to 2.0 cm.sup.3/g.

10. The porous shaped body according to claim 1, wherein the modal pore diameter measured by a mercury intrusion method is from 0.08 m to 0.7 m.

11. The porous shaped body according to claim 1, wherein the anion concentration in an aqueous solution prepared by immersing the porous shaped body in pure water in an amount 10 times the bulk volume of the same at 70 C. for 1 hour is less than 2.0 mg/L.

12. The porous shaped body according to claim 1, wherein the value of absorbance in a UV measurement of an aqueous solution prepared by immersing the porous shaped body in pure water in an amount 10 times the bulk volume of the same at 70 C. for 1 hour is less than 0.2.

13. The porous shaped body according to claim 1, wherein the metal ion concentration in an aqueous solution prepared by immersing the porous shaped body in pure water in an amount 10 times the bulk volume of the same at 70 C. for 1 hour is less than 1.0 mg/L.

14. The porous shaped body according to claim 1, wherein the pH of an aqueous solution prepared by immersing the porous shaped body in pure water in an amount 10 times the bulk volume of the same at 70 C. for 1 hour is 5 or more, and the amount of change in pH is from 0 to 1.5.

15. The porous shaped body according to claim 1, wherein the abrasion rate of the porous shaped body is from 0% to 0.1%.

16. The porous shaped body according to claim 1, wherein the inorganic ion adsorbent comprises at least one metal oxide represented by the following Formula (I):
MN.sub.xO.sub.n.Math.mH.sub.2O (I) [wherein x is 0 to 3, n is 1 to 4, m is 0 to 6, and M and N are metal elements that are different from each other, and selected from the group consisting of Ti, Zr, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, Cr, Co, Ga, Fe, Mn, Ni, V, Ge, Nb, and Ta]; and/or at least one metal carbonate represented by the following Formula (III):
Q.sub.yR.sub.z(CO.sub.3).sub.s.Math.tH.sub.2O (III) [wherein y is 1 to 2, z is 0 to 1, s is 1 to 3, t is 0 to 8, and Q and R are metal elements that are different from each other, and selected from the group consisting of Mg, Ca , Sr, Ba, Sc, Mn, Fe, Co, Ni, Ag, Zn, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu].

17. The porous shaped body according to claim 16, wherein the metal oxide is selected from the following groups (a) to (c): (a) hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide, and hydrated yttrium oxide; (b) a composite metal oxide between at least one metal element selected from the group consisting of titanium, zirconium, tin, cerium, lanthanum, and yttrium, and at least one metal element selected from the group consisting of aluminum, silicon, and iron; and (c) activated alumina.

18. The porous shaped body according to claim 16, wherein the metal carbonate is selected from the following group (d): (d) magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, scandium carbonate, manganese carbonate, iron carbonate, cobalt carbonate, nickel carbonate, silver carbonate, zinc carbonate, yttrium carbonate, lanthanum carbonate, cerium carbonate, praseodymium carbonate, neodymium carbonate, samarium carbonate, europium carbonate, gadolinium carbonate, terbium carbonate, dysprosium carbonate, holmium carbonate, erbium carbonate, thulium carbonate, ytterbium carbonate, and lutetium carbonate.

19. The porous shaped body according to claim 1, wherein the organic polymer resin is at least one selected from the group consisting of an ethylene/vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polysulfone (PS), polyethersulfone (PES), poly(vinylidene fluoride) (PVDF), poly(methyl methacrylate) (PMMA), poly(aryl ether sulfone), polypropylene, polystyrene, polycarbonate, cellulose, and cellulose triacetate.

Description

EXAMPLES

(1) The present invention will be specifically described below with reference to Examples and Comparative Examples, provided that the present invention is not limited thereto. The physical properties of a shaped body were measured by the following methods.

(2) (1) Pore Volume, and Specific Surface Area Measured by Nitrogen Gas Adsorption Method

(3) A porous shaped body was freeze-dried and then measured with a specific surface area and pore size distribution measuring device (BELSORP-MINI II (trade name), manufactured by MicrotracBEL Corp.).

(4) About 0.3 g of a freeze-dried porous shaped body was weighed, and placed in a dedicated 5 mL glass cell. Measurements of the pore volume and the specific surface area were carried out by adsorption and desorption of a nitrogen gas, while cooling the glass cell with liquid nitrogen.

(5) A nitrogen gas having a purity of 99.99% by volume or higher was used as the adsorbate, and a helium gas having a purity of 99.99% by volume or higher was used as the purge gas.

(6) As a reference cell, an empty glass cell having the same volume as the glass cell for measurement was used, and a measurement was performed with the setting that the measured value should be corrected.

(7) Measurements were conducted by a simplified measurement method with the setting that the upper limit of the adsorption relative pressure was 0.95, and the lower limit of the desorption relative pressure was 0.3.

(8) The analyses by the BET method and the BJH method after the measurement were performed using an analysis software (BEL Master (Version 6.3.1.0), produced by MicrotracBEL Corp.).

(9) (2) Freeze-Drying of Porous Shaped Body

(10) Freeze-drying was performed using a freeze-drying machine (FDS-1000 (trade name) manufactured by EYELA).

(11) From 1 to 10 mL of a porous shaped body in a wet state was measured with a graduated cylinder or the like, and placed in a 100 mL glass recovery flask, which was then left standing in a freezer at 18 C. or lower for 6 hours or longer to freeze moisture contained. Then the recovery flask was connected with the freeze-drying machine to perform freeze-drying for 10 hours under the conditions that the degree of vacuum was 20 Pa or less, and a trap temperature was 80 C. or less.

(12) (3) Average Particle Diameter of Porous Shaped Body, and Average Particle Diameter of Inorganic Ion Adsorbent

(13) The average particle diameter of a porous shaped body and the average particle diameter of an inorganic ion adsorbent were measured with a laser diffraction/scattering particle size analyzer (LA-950 (trade name) manufactured by Horiba, Ltd.). Water was used as a dispersion medium. In the measurement of a sample using hydrated cerium oxide as the inorganic ion adsorbent, the measurement was performed using the value of cerium oxide for the refractive index. Similarly, in the measurement of a sample using hydrated zirconium oxide as the inorganic ion adsorbent, the measurement was performed using the value of zirconium oxide for the refractive index.

(14) (4) Pore Volume and Modal Pore Diameter of Porous Shaped Body Measured by Mercury Intrusion Method,

(15) A porous shaped body was freeze-dried by the aforedescribed method, and then measured with a mercury porosimeter (Shimadzu AutoPore IV 9500, manufactured by Shimadzu Corporation).

(16) (5) Elastic Modulus of Porous Shaped Body

(17) An elastic modulus was measured with a compression-type elastic modulus measuring device (EZ-Test-500N (trade name) manufactured by Shimadzu Corporation). Using a graduated cylinder or the like, 1 mL-bulk volume of a porous shaped body in a wet state was measured, placed in a dedicated 1 mL cell, compressed with a cylindrical compression jig with a diameter of 10 mm at a stroke velocity of 1 mm/min. Then, a measurement was performed thereon.

(18) (6) Measurement of Viscosity of Slurry

(19) Step (3): The viscosity of a slurry prepared in the step of preparing a slurry was measured by placing the slurry in a cylindrical container having a diameter of 50 mm and a depth of 70 mm after regulating the temperature within 25 C. 1 C., and using a B-type viscometer (RB-85L (trade name) manufactured by Toki Sangyo Co., Ltd.). A viscosity measurement was performed, where a rotor No. 3 (trade name) was use, and the rotation velocity was 0.3 rpm to 60 rpm.

(20) (7) Measurement of Anion Concentration

(21) A porous shaped body was immersed in water in an amount 10 times the bulk volume of the same at 70 C. for 1 hour, and the anion concentrations in the water after the immersion were measured by ion chromatography (DIONEXICS-2100 (trade name), manufactured by ThremoSCIENTIFIC). The sum total of the concentration of each anion species was calculated and defined as the anion concentration. Measurements of a phosphate ion, a sulfate ion, a nitrite ion, a bromide ion, a nitrate ion, a fluoride ion, and a chloride ions were performed using Anion Mixture Standard Solution 1 (product name, FUJIFILM Wako Pure Chemical Corporation) as the standard solution.

(22) (8) Measurement of Metal Concentration

(23) A porous shaped body was immersed in water in an amount 10 times the bulk volume of the same at 70 C. for 1 hour, and the metal concentration in the water after the immersion was measured by an inductively-coupled plasma mass spectrometer (iCAPQ (trade name) manufactured by ThremoSCIENTIFIC). As the standard solution, a standard solution containing a metal element ion constituting an inorganic ion adsorbent was used. For example, when an inorganic ion adsorbent is hydrated cerium oxide, a Cerium Standard Solution (1,000 ppm) (product name, FUJIFILM Wako Pure Chemical Corporation) was used.

(24) (9) Measurement of UV Absorbance

(25) A porous shaped body was immersed in water in an amount 10 times the bulk volume of the same at 70 C. for 1 hour, and the liquid after the immersion was placed in a quartz glass cell having an optical path length of 1 cm, which absorbance was measured in a wavelength range of 200 nm to 350 nm using a UV-Vis spectrophotometer (UV-2400PC manufactured by Shimadzu Corporation). The maximum value of absorbance was regarded as a measured value.

(26) (10) Measurement of pH and Amount of Change of pH

(27) A porous shaped body was immersed in water in an amount 10 times the bulk volume of the same at 70 C. for 1 hour, and pH was measured on the liquid after the immersion with a pH meter (pH/Cond Meter D-54 manufactured by Horiba, Ltd.).

(28) The amount of change of pH was defined as the absolute value of the difference between the above measured value and the value obtained by a measurement with a pH meter with respect to the liquid prepared by heating the same amount of pure water at 70 C. for 1 hour.

(29) (11) Abrasion Rate

(30) As for an abrasion rate, 5 mL of a porous shaped body and 50 mL of pure water were charged into a 100 mL container having a height of 5 to 10 cm, and reciprocating shaking was performed thereon at a velocity of 250 rpm for 30 min. The supernatant liquid was filtrated with suction using a 0.2 m filter, and the dry weight of the obtained abraded component Wd, and the dry weight of 5 mL of the porous shaped body after the reciprocating shaking We were weighed, and the abrasion rate was determined according to the following Formula:
Abrasion rate (%)=[Wd/(We+Wd)]100

(31) When the abrasion rate was less than 0.1% by mass, it was judged that abrasion was little and rated good.

(32) (12) Pressure Loss

(33) A column having an inner diameter of 20 mm and a height of 500 mm was filled with 60 mL of a porous shaped body. Pure water was fed to flow from the top to the bottom of the column at a velocity of LV 20 m/hr, and the difference (A (kPa)) between the inlet pressure and the outlet pressure was measured. Then, pure water was fed to flow from the top to the bottom of the empty column without the adsorbent at a velocity of LV 20 m/hr, and the difference (B (kPa)) between the inlet pressure and the outlet pressure was measured. Measuring the fill height (H) of the adsorbent, a pressure loss (AB)/H (kPa/m) was calculated.

(34) When the value of a pressure loss was less than 50 kPa/m, it was judged that the pressure rise was small and rated good.

(35) (13) Adsorption Amount of Phosphorus

(36) Trisodium phosphate (Na.sub.3PO.sub.4.Math.12H.sub.2O) was dissolved in distilled water to prepare a solution with a phosphorus concentration of 9 mg-P/L, and the solution was adjusted to pH 7 with sulfuric acid, and used as an adsorption stock liquid.

(37) A column (inner diameter 10 mm) was filled with 8 mL of porous shaped body measured using a graduated cylinder with repeated tapping, to which the adsorption stock liquid was fed to flow at a velocity of 960 mL/hr (SV 120 hr.sup.1), and 1,920 mL/hr (SV 240 hr.sup.1) respectively.

(38) The effluent (treated liquid) from the column was sampled every 10 min, and the phosphorus concentration in the treated water was measured, and the total adsorbed mass (g-P/L-porous shaped body) during a 4-hour flow was determined.

(39) A phosphate ion concentration was measured using a phosphoric acid measuring device (PHOSPHAX Compact (trade name) manufactured by Hach Company).

(40) When the total adsorbed mass of phosphorus at the velocity of SV 120 hr.sup.1 was 1.8 (g-P/L-porous shaped body) or more, it was rated that the porous shaped body had a high adsorption capacity, and was excellent as a phosphorus adsorbent. When it was 2.5 (g-P/L-porous shaped body) or more, it was rated even better.

Example 11

(41) In 50 L of pure water, 2000 g of cerium sulfate tetrahydrate (Wako Pure Chemical Industries, Ltd.) was added and dissolved using a stirring blade, and then 3 L of 8M caustic soda (Wako Pure Chemical Industries, Ltd.) was dropped thereto at a rate of 20 mL/min. As a result, a precipitate of hydrated cerium oxide was yielded. The yielded precipitate was filtered with a filter press, irrigating the same with 500 L of pure water, and successively with 80 L of ethanol (Wako Pure Chemical Industries, Ltd.) to replace the water contained in hydrated cerium oxide with ethanol. At this time, 10 mL of the filtrate at the end of the filtration was sampled, and its water content was analyzed with a Karl Fisher water content meter (CA-200 (trade name) manufactured by Mitsubishi Chemical Analytech Co., Ltd.) to find that the water content was 5% by mass, and the replacement rate with the organic liquid was 95% by mass. The obtained hydrated cerium oxide containing the organic liquid was air-dried to obtain dried hydrated cerium oxide.

(42) The obtained dry hydrated cerium oxide was pulverized using a jet mill (SJ-100 (trade name), manufactured by Nisshin Engineering Inc.) under the conditions of a compressed air pressure of 0.8 MPa and a raw material feed rate of 100 g/hr.

(43) A uniform shaping slurry solution was yielded by charging 220 g of N-methyl-2-pyrrolidone (NMP, Mitsubishi Chemical Corporation), 150 g of a ground hydrated cerium oxide powder, and 40 g of polyethersulfone in a dissolving tank, and then heating the content to 60 C. to be dissolved with stirring using a stirring blade.

(44) The yielded shaping slurry was supplied into a cylindrical rotating container having nozzle holes with a diameter of 4 mm opened on the side surface, the container was rotated to form liquid droplets through the nozzle holes by a centrifugal force (15 G). The droplets were made to land and solidified on an open top surface of a solidifying tank storing a solidifying liquid which contained NMP at 50% by mass with respect to water, and was heated to 60 C.

(45) The solidified porous shaped body was recovered, and a column having an inner diameter of 20 mm) was filled with 150 mL of the porous shaped body. For alkali washing, 1500 mL of a 0.4 wt % aqueous solution of sodium hydroxide heated to 70 C. was fed to the column to flow from the top to the bottom at SV 10 hr.sup.1. Further, washing with water was conducted by feeding 450 L of pure water to the column to flow from the top to the bottom at SV 80 hr.sup.1 thereby obtaining a cleaned porous shaped body.

Example 2

(46) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the feeding amount of ethanol was changed to 60 L, and the replacement rate with the organic liquid was changed to 83% by mass.

Example 3

(47) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the feeding amount of ethanol was changed to 40 L, and the replacement rate with the organic liquid was changed to 72% by mass.

Example 4

(48) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the feeding amount of ethanol was changed to 20 L, and the replacement rate with the organic liquid was changed to 54% by mass.

Example 5

(49) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that 5 g of polyvinylpyrrolidone (PVP, produced by BASF) was added as a water-soluble polymer to the slurry.

Example 6

(50) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the amount of the hydrated cerium oxide powder was changed to 300 g.

Example 7

(51) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the amount of the hydrated cerium oxide powder was changed to 120 g.

Example 8

(52) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the amount of the hydrated cerium oxide powder was changed to 80 g.

Example 9

(53) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the amount of the hydrated cerium oxide powder was changed to 50 g.

Example 10

(54) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the amount of the hydrated cerium oxide powder was changed to 40 g.

Example 11

(55) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the amount of the hydrated cerium oxide powder was changed to 30 g.

Example 12

(56) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the amount of the hydrated cerium oxide powder was changed to 20 g.

Example 13

(57) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the amount of the hydrated cerium oxide powder was changed to 17 g.

Example 14

(58) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the diameter of the nozzle was changed to 3.5 mm.

Example 15

(59) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the diameter of the nozzle was changed to 3.0 mm.

Example 16

(60) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the amount of N-methyl-2-pyrrolidone was changed to 240 g and the diameter of the nozzle was changed to 4.5 mm.

Example 17

(61) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that sodium dodecyl sulfate (Wako Pure Chemical Industries, Ltd.) was added to the poor solvent at a concentration of 2,000 mg/L.

Example 18

(62) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that a solidifying liquid containing NMP at 60% by mass with respect to water was used.

Example 19

(63) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the temperature of the solidifying liquid was changed to 80 C.

Example 20

(64) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the amount of N-methyl-2-pyrrolidone was changed to 250 g and the diameter of the nozzle was changed to 3.5 mm.

Example 21

(65) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the solidifying liquid was changed to water, namely the solidifying liquid with an NMP content of 0% by mass with respect to water was used.

Example 22

(66) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the temperature of the solidifying liquid was changed to 25 C.

Example 23

(67) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the temperature of the solidifying liquid was changed to 25 C., and the solidifying liquid was changed to water, namely the solidifying liquid with an NMP content of 0% by mass with respect to water was used.

Example 24

(68) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the diameter of the nozzle was changed to 2.5 mm.

Example 25

(69) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the diameter of the nozzle was changed to 5.0 mm.

Example 26

(70) A spherical porous shaped body was obtained in the same manner as described in Example 10 except that the temperature of the solidifying liquid was changed to 80 C.

Example 27

(71) A spherical porous shaped body was obtained in the same manner as described in Example 10 except that the temperature of the solidifying liquid was changed to 80 C., and its NMP content with respect to water was changed to 60% by mass.

Example 28

(72) A spherical porous shaped body was obtained in the same manner as described in Example 10 except that the amount of N-methyl-2-pyrrolidone was changed to 180 g.

Example 29

(73) A spherical porous shaped body was obtained in the same manner as described in Example 10 except that the amount of N-methyl-2-pyrrolidone was changed to 140 g.

Example 30

(74) A spherical porous shaped body was obtained in the same manner as described in Example 10 except that the content of NMP in the solidifying liquid with respect to water was changed to 0% by mass.

Example 31

(75) A spherical porous shaped body was obtained in the same manner as described in Example 10 except that the content of NMP in the solidifying liquid with respect to water was changed to 0% by mass, and further the temperature was changed to 25 C.

Example 32

(76) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the pressure of the compressed air was changed to 0.6 MPa when hydrated cerium oxide was pulverized using a jet mill.

Example 33

(77) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the pressure of the compressed air was changed to 0.5 MPa when hydrated cerium oxide was pulverized using a jet mill, and the raw material feed rate was changed to 200 g/hr.

Example 34

(78) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the pressure of the compressed air was changed to 0.9 MPa when hydrated cerium oxide was pulverized using a jet mill, and the raw material feed rate was changed to 50 g/hr.

Example 35

(79) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the method for pulverizing the hydrated cerium oxide obtained by air-drying was changed to wet ball mill pulverization in preparing a slurry. In the ball mill pulverization, 150 g of the hydrated cerium oxide obtained by air-drying, and 220 g of N-methyl-2-pyrrolidone were charged into a 1 L-stainless steel ball mill pot filled with 1.5 kg of stainless steel balls with a diameter of 5 mm, and pulverizing and mixing operation was performed at a rotation rate of 150 rpm for 150 min to obtain a yellow slurry. In a dissolving tank, 40 g of polyethersulfone was added to the obtained slurry, and the mixture was heated to 60 C. and stirred using a stirring blade to be dissolved and form a uniform shaping slurry.

Example 36

(80) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the method for pulverizing hydrated cerium oxide was changed to a method in which pulverization was performed with a mortar for 5 min.

Example 3

(81) A spherical porous shaped body was obtained in the same manner as described in Example 35 except that the pulverization time in pulverizing the hydrated cerium oxide obtained by air drying by wet ball mill pulverization was changed to 60 min.

Example 38

(82) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the concentration of the aqueous solution of sodium hydroxide used for washing was changed to 1.0 wt %.

Example 39

(83) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the concentration of the aqueous solution of sodium hydroxide used for washing was changed to 0.1 wt %.

Example 40

(84) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the raw material for an inorganic ion adsorbent was changed to cerium (III) chloride heptahydrate (Wako Pure Chemical Industries, Ltd.).

Example 41

(85) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that washing with the aqueous solution of sodium hydroxide was not carried out.

Example 42

(86) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that washing with the aqueous solution of sodium hydroxide and pure water was not carried out.

Comparative Example 1

(87) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the feeding amount of ethanol was changed to 4 L and the replacement rate with the organic liquid was 14% by mass.

Comparative Example 2

(88) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the feeding amount of ethanol was changed to 0 L and the replacement rate with the organic liquid was changed to 0% by mass.

Comparative Example 3

(89) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the feeding amount of ethanol was changed to 0 L, the replacement rate with an organic liquid was changed to 0% by mass, and the hydrated cerium oxide powder was set at 500 g.

Comparative Example 4

(90) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the addition amount of the hydrated cerium oxide powder was changed to 0 g.

Comparative Example 5

(91) A spherical porous shaped body was obtained in the same manner as described in Example 1 except that the compressed air pressure was changed to 0.9 MPa, and the raw material feed rate was changed to 20 g/hr.

Comparative Example 6

(92) A spherical porous shaped body was obtained in the same manner as described in Example 35 except that the pulverization time in pulverizing the hydrated cerium oxide obtained by air drying by wet ball mill pulverization was changed to 600 min.

Comparative Example 7

(93) A spherical porous shaped body was obtained in the same manner as described in Comparative Example 1 except that washing with the aqueous solution of sodium hydroxide was not performed.

(94) The physical properties, etc. of the porous shaped bodies obtained in Examples 1 to 42, and Comparative Examples 1 to 7 are shown in Table 1 below ([Table 1-2], [Table 1-3], [Table 1-4], and [Table 1-5] are continuations of [Table 1-1].)

(95) TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- ple 1 ple 2 ple 3 ple 4 ple 5 Organic polymer resin PES PES PES PES PES Water-soluble polymer PVP Inorganic ion adsorbent Sul- Sul- Sul- Sul- Sul- raw material fate fate fate fate fate Inorganic ion adsorbent C C C C C Replacement rate with 95 83 72 54 95 ethanol in inorganic ion adsorbent (% by mass) Supported amount of 79 79 79 79 79 inorganic ion adsorbent (% by mass) Sum total of pore volumes 0.39 0.25 0.18 0.09 0.38 per unit mass of inorganic ion adsorbent measured by nitrogen gas adsorption method (cm.sup.3/g) Pulverization method of Jet Jet Jet Jet Jet inorganic ion exchanger mill mill mill mill mill Average particle diameter 1.03 0.98 1.01 1.05 1.03 of inorganic ion adsorbent (m) Ratio of (maximum particle 67 77 80 75 67 diameter)/(minimum particle diameter) of inorganic ion adsorbent Viscosity of stock liquid 2074 1964 1855 1808 3566 (mPa .Math. s) Granulation by rotating Possi- Possi- Possi- Possi- Possi- nozzle method ble ble ble ble ble Solidification tank 60 60 60 60 60 temperature ( C.) NMP concentration in 50 50 50 50 50 solidification tank (% by mass) Concentration of surfactant 0 0 0 0 0 added to solidification tank (mg/L) Nozzle diameter (mm) 4 4 4 4 4 Average particle diameter 545 535 541 544 549 of porous shaped body (m) Pore volume of porous shaped 0.31 0.20 0.14 0.09 0.30 body measured by nitrogen gas adsorption method (cm.sup.3/g) Specific surface area of 224 168 134 98 193 porous shaped body measured by nitrogen gas adsorption method (m.sup.2/g) Flatness ratio of porous 0.10 0.12 0.11 0.11 0.02 shaped body Bulk density of porous 0.51 0.49 0.49 0.51 0.50 shaped body (g/mL-porous shaped body) Pore volume measured by 1.11 1.07 1.03 1.04 1.02 mercury intrusion method (cm.sup.3/g) Modal pore diameter 0.14 0.12 0.13 0.13 0.25 measured by mercury intrusion method (m) Elastic modulus of porous 6250 6140 6022 6102 6203 shaped body (mN/m.sup.2) Abrasion rate of porous 0.02 0.03 0.04 0.08 0.07 shaped body (% by mass) Sodium hydroxide 0.4 0.4 0.4 0.4 0.4 concentration at the time of washing (% by mass) Sodium hydroxide feed 10 10 10 10 10 amount at the time of washing (times) Sodium hydroxide flow rate 10 10 10 10 10 at the time of washing (h.sup.1) Pure water feed amount at 300 300 300 300 300 the time of washing (times) Pure water feed rate at 80 80 80 80 80 the time of washing (h.sup.1) Leached anion concentration 0.2 0.1 0.2 0.1 0.0 (mg/L) UV absorbance 0.00 0.00 0.00 0.01 0.15 Leached metal ion <0.0001 <0.0001 <0.0001 0.0003 <0.0001 concentration (mg/L) pH 6.0 6.2 6.6 6.3 6.1 pH change amount 0.2 0.3 0.5 0.3 0.2 Pressure loss at LV 20 24 25 22 26 18 m/hr (kPa/m) Phosphorus adsorption amount 3.76 3.50 3.27 2.42 4.11 (g-P/L- porous shaped body), SV120 h.sup.1 Phosphorus adsorption amount 4.21 3.92 3.66 2.98 4.64 (g-P/L- porous shaped body), SV240 h.sup.1 Exam- Exam- Exam- Exam- Exam- ple 6 ple 7 ple 8 ple 9 ple 10 Organic polymer resin PES PES PES PES PES Water-soluble polymer Inorganic ion adsorbent Sul- Sul- Sul- Sul- Sul- raw material fate fate fate fate fate Inorganic ion adsorbent C C C C C Replacement rate with 95 95 95 95 95 ethanol in inorganic ion adsorbent (% by mass) Supported amount of 88 75 67 56 50 inorganic ion adsorbent (% by mass) Sum total of pore volumes 0.36 0.36 0.34 0.36 0.35 per unit mass of inorganic ion adsorbent measured by nitrogen gas adsorption method (cm.sup.3/g) Pulverization method of Jet Jet Jet Jet Jet inorganic ion exchanger mill mill mill mill mill Average particle diameter 1.03 1.03 1.03 1.03 1.03 of inorganic ion adsorbent (m) Ratio of (maximum particle 67 67 67 67 67 diameter)/(minimum particle diameter) of inorganic ion adsorbent Viscosity of stock liquid 3251 2003 1713 1608 1531 (mPa .Math. s) Granulation by rotating Possi- Possi- Possi- Possi- Possi- nozzle method ble ble ble ble ble Solidification tank 60 60 60 60 60 temperature ( C.) NMP concentration in 50 50 50 50 50 solidification tank (% by mass) Concentration of surfactant 0 0 0 0 0 added to solidification tank (mg/L) Nozzle diameter (mm) 4 4 4 4 4 Average particle diameter 537 544 554 548 551 of porous shaped body (m) Pore volume of porous shaped 0.32 0.27 0.23 0.20 0.18 body measured by nitrogen gas adsorption method (cm.sup.3/g) Specific surface area of 194 212 207 191 211 porous shaped body measured by nitrogen gas adsorption method (m.sup.2/g) Flatness ratio of porous 0.03 0.13 0.21 0.22 0.25 shaped body Bulk density of porous 0.59 0.45 0.41 0.34 0.32 shaped body (g/mL-porous shaped body) Pore volume measured by 0.68 1.23 1.28 1.31 1.35 mercury intrusion method (cm.sup.3/g) Modal pore diameter 0.14 0.16 0.18 0.18 0.21 measured by mercury intrusion method (m) Elastic modulus of porous 8102 5551 4203 3408 3098 shaped body (mN/m.sup.2) Abrasion rate of porous 0.17 0.02 0.00 0.00 0.00 shaped body (% by mass) Sodium hydroxide 0.4 0.4 0.4 0.4 0.4 concentration at the time of washing (% by mass) Sodium hydroxide feed 10 10 10 10 10 amount at the time of washing (times) Sodium hydroxide flow rate 10 10 10 10 10 at the time of washing (h.sup.1) Pure water feed amount at 300 300 300 300 300 the time of washing (times) Pure water feed rate at 80 80 80 80 80 the time of washing (h.sup.1) Leached anion concentration 0.3 0.2 0.2 0.1 0.0 (mg/L) UV absorbance 0.04 0.00 0.00 0.00 0.00 Leached metal ion 0.0012 <0.0001 <0.0001 <0.0001 <0.0001 concentration (mg/L) pH 6.3 6.2 6.0 6.9 5.8 pH change amount 0.2 0.3 0.1 0.7 0.0 Pressure loss at LV 20 26 32 36 37 41 m/hr (kPa/m) Phosphorus adsorption amount 3.88 3.62 3.33 3.11 2.97 (g-P/L- porous shaped body), SV120 h.sup.1 Phosphorus adsorption amount 4.42 4.16 3.63 3.61 3.42 (g-P/L- porous shaped body), SV240 h.sup.1 Exam- Exam- Exam- Exam- Exam- ple 11 ple 12 ple 13 ple 14 ple 15 Organic polymer resin PES PES PES PES PES Water-soluble polymer Inorganic ion adsorbent Sul- Sul- Sul- Sul- Sul- raw material fate fate fate fate fate Inorganic ion adsorbent C C C C C Replacement rate with 95 95 95 95 95 ethanol in inorganic ion adsorbent (% by mass) Supported amount of 43 33 31 79 79 inorganic ion adsorbent (% by mass) Sum total of pore volumes 0.36 0.34 0.35 0.34 0.36 per unit mass of inorganic ion adsorbent measured by nitrogen gas adsorption method (cm.sup.3/g) Pulverization method of Jet Jet Jet Jet Jet inorganic ion exchanger mill mill mill mill mill Average particle diameter 1.03 1.03 1.03 1.03 1.03 of inorganic ion adsorbent (m) Ratio of (maximum particle 67 67 67 67 67 diameter)/(minimum particle diameter) of inorganic ion adsorbent Viscosity of stock liquid 1247 1032 828 1999 2084 (mPa .Math. s) Granulation by rotating Possi- Possi- Possi- Possi- Possi- nozzle method ble ble ble ble ble Solidification tank 60 60 60 60 60 temperature ( C.) NMP concentration in 50 50 50 50 50 solidification tank (% by mass) Concentration of surfactant 0 0 0 0 0 added to solidification tank (mg/L) Nozzle diameter (mm) 4 4 4 3.5 3 Average particle diameter 546 543 533 450 352 of porous shaped body (m) Pore volume of porous shaped 0.15 0.11 0.11 0.27 0.28 body measured by nitrogen gas adsorption method (cm.sup.3/g) Specific surface area of 205 195 189 217 198 porous shaped body measured by nitrogen gas adsorption method (m.sup.2/g) Flatness ratio of porous 0.29 0.30 0.41 0.11 0.06 shaped body Bulk density of porous 0.29 0.28 0.24 0.50 0.49 shaped body (g/mL-porous shaped body) Pore volume measured by 1.42 1.51 1.55 1.03 1.19 mercury intrusion method (cm.sup.3/g) Modal pore diameter measured 0.23 0.26 0.19 0.19 0.18 by mercury intrusion method (m) Elastic modulus of porous 2487 2111 1722 6003 5244 shaped body (mN/m.sup.2) Abrasion rate of porous 0.00 0.00 0.00 0.02 0.01 shaped body (% by mass) Sodium hydroxide 0.4 0.4 0.4 0.4 0.4 concentration at the time of washing (% by mass) Sodium hydroxide feed 10 10 10 10 10 amount at the time of washing (times) Sodium hydroxide flow 10 10 10 10 10 rate at the time of washing (h.sup.1) Pure water feed amount 300 300 300 300 300 at the time of washing (times) Pure water feed rate at 80 80 80 80 80 the time of washing (h.sup.1) Leached anion 0.1 0.0 0.0 0.3 0.0 concentration (mg/L) UV absorbance 0.00 0.00 0.00 0.02 0.00 Leached metal ion <0.0001 <0.0001 <0.0001 0.0005 <0.0001 concentration (mg/L) pH 6.0 6.0 6.2 6.3 6.2 pH change amount 0.1 0.1 0.3 0.4 0.2 Pressure loss at LV 20 46 49 59 38 47 m/hr (kPa/m) Phosphorus adsorption amount 2.68 2.38 1.99 4.01 4.17 (g-P/L- porous shaped body), SV120 h.sup.1 Phosphorus adsorption amount 3.11 2.85 2.43 4.41 4.59 (g-P/L- porous shaped body), SV240 h.sup.1 Exam- Exam- Exam- Exam- Exam- ple 16 ple 17 ple 18 ple 19 ple 20 Organic polymer resin PES PES PES PES PES Water-soluble polymer Inorganic ion adsorbent Sul- Sul- Sul- Sul- Sul- raw material fate fate fate fate fate Inorganic ion adsorbent C C C C C Replacement rate with 95 95 95 95 95 ethanol in inorganic ion adsorbent (% by mass) Supported amount of 79 79 79 79 79 inorganic ion adsorbent (% by mass) Sum total of pore volumes 0.36 0.36 0.36 0.36 0.34 per unit mass of inorganic ion adsorbent measured by nitrogen gas adsorption method (cm3/g) Pulverization method of Jet Jet Jet Jet Jet inorganic ion exchanger mill mill mill mill mill Average particle diameter 1.03 1.03 1.03 1.03 1.03 of inorganic ion adsorbent (m) Ratio of (maximum particle 67 67 67 67 67 diameter)/(minimum particle diameter) of inorganic ion adsorbent Viscosity of stock liquid 1898 1902 1952 1970 1122 (mPa .Math. s) Granulation by rotating Possi- Possi- Possi- Possi- Possi- nozzle method ble ble ble ble ble Solidification tank 60 60 60 80 60 temperature ( C.) NMP concentration in 50 50 60 50 50 solidification tank (% by mass) Concentration of surfactant 0 2000 0 0 0 added to solidification tank (mg/L) Nozzle diameter (mm) 4.5 4 4 4 3.5 Average particle diameter 672 542 544 540 448 of porous shaped body (m) Pore volume of porous shaped 0.28 0.28 0.28 0.28 0.27 body measured by nitrogen gas adsorption method (cm3/g) Specific surface area of 212 220 212 215 222 porous shaped body measured by nitrogen gas adsorption method (m2/g) Flatness ratio of porous 0.28 0.05 0.04 0.04 0.52 shaped body Bulk density of porous 0.47 0.50 0.51 0.51 0.41 shaped body (g/mL-porous shaped body) Pore volume measured by 1.11 1.13 1.08 1.21 0.97 mercury intrusion method (cm3/g) Modal pore diameter measured 0.16 0.22 0.35 0.32 0.22 by mercury intrusion method (m) Elastic modulus of porous 5181 5790 5736 5783 4888 shaped body (mN/m2) Abrasion rate of porous 0.03 0.00 0.01 0.00 0.13 shaped body (% by mass) Sodium hydroxide 0.4 0.4 0.4 0.4 0.4 concentration at the time of washing (% by mass) Sodium hydroxide feed 10 10 10 10 10 amount at the time of washing (times) Sodium hydroxide flow 10 10 10 10 10 rate at the time of washing (h1) Pure water feed amount 300 300 300 300 300 at the time of washing (times) Pure water feed rate at 80 80 80 80 80 the time of washing (h1) Leached anion 0.1 0.0 0.1 0.0 1.0 concentration (mg/L) UV absorbance 0.00 0.00 0.00 0.00 0.07 Leached metal ion <0.0001 <0.0001 <0.0001 <0.0001 0.0017 concentration (mg/L) pH 5.9 6.2 6.0 5.9 6.2 pH change amount 0.1 0.4 0.1 0.0 0.3 Pressure loss at LV 20 39 20 21 21 68 m/hr (kPa/m) Phosphorus adsorption amount 2.74 3.62 3.59 3.60 4.01 (g-P/L- porous shaped body), SV120 h1 Phosphorus adsorption amount 3.03 3.99 3.90 3.94 4.53 (g-P/L- porous shaped body), SV240 h1 Exam- Exam- Exam- Exam- Exam- ple 21 ple 22 ple 23 ple 24 ple 25 Organic polymer resin PES PES PES PES PES Water-soluble polymer Inorganic ion adsorbent Sul- Sul- Sul- Sul- Sul- raw material fate fate fate fate fate Inorganic ion adsorbent C C C C C Replacement rate with ethanol 95 95 95 95 95 in inorganic ion adsorbent (% by mass) Supported amount of inorganic 79 79 79 79 79 ion adsorbent (% by mass) Sum total of pore volumes per 0.33 0.33 0.33 0.34 0.36 unit mass of inorganic ion adsorbent measured by nitrogen gas adsorption method (cm.sup.3/g) Pulverization method of Jet Jet Jet Jet Jet inorganic ion exchanger mill mill mill mill mill Average particle diameter of 1.03 1.03 1.03 1.03 1.03 inorganic ion adsorbent (m) Ratio of (maximum particle 67 67 67 67 67 diameter)/(minimum particle diameter) of inorganic ion adsorbent Viscosity of stock liquid 2100 1934 1987 1901 1977 (mPa .Math. s) Granulation by rotating Possi- Possi- Possi- Possi- Possi- nozzle method ble ble ble ble ble Solidification tank 60 25 25 60 60 temperature ( C.) NMP concentration in 0 50 0 50 50 solidification tank (% by mass) Concentration of surfactant 0 0 0 0 0 added to solidification tank (mg/L) Nozzle diameter (mm) 4 4 4 2.5 5 Average particle diameter 552 522 557 257 806 of porous shaped body (m) Pore volume of porous shaped 0.26 0.26 0.26 0.27 0.28 body measured by nitrogen gas adsorption method (cm.sup.3/g) Specific surface area of 221 218 207 195 192 porous shaped body measured by nitrogen gas adsorption method (m.sup.2/g) Flatness ratio of porous 0.55 0.41 0.67 0.09 0.13 shaped body Bulk density of porous 0.50 0.52 0.51 0.49 0.49 shaped body (g/mL-porous shaped body) Pore volume measured by 1.02 0.96 0.79 1.07 1.08 mercury intrusion method (cm.sup.3/g) Modal pore diameter measured 0.12 0.08 0.09 0.12 0.11 by mercury intrusion method (m) Elastic modulus of porous 6776 7598 7322 6021 6053 shaped body (mN/m.sup.2) Abrasion rate of porous 0.09 0.11 0.21 0.00 0.01 shaped body (% by mass) Sodium hydroxide 0.4 0.4 0.4 0.4 0.4 concentration at the time of washing (% by mass) Sodium hydroxide feed 10 10 10 10 10 amount at the time of washing (times) Sodium hydroxide flow rate 10 10 10 10 10 at the time of washing (h.sup.1) Pure water feed amount at 300 300 300 300 300 the time of washing (times) Pure water feed rate at the 80 80 80 80 80 time of washing (h.sup.1) Leached anion concentration 0.1 0.2 1.6 0.1 0.1 (mg/L) UV absorbance 0.14 0.05 0.11 0.00 0.00 Leached metal ion <0.0001 0.0009 0.010 <0.0001 <0.0001 concentration (mg/L) pH 6.6 6.8 6.9 6.3 6.5 pH change amount 0.6 0.9 0.8 0.3 0.6 Pressure loss at LV 20 52 55 69 136 14 m/hr (kPa/m) Phosphorus adsorption amount 3.31 3.5 3.97 4.31 1.84 (g-P/L- porous shaped body), SV120 h.sup.1 Phosphorus adsorption amount 3.74 3.87 4.48 4.71 2.02 (g-P/L- porous shaped body), SV240 h.sup.1 Exam- Exam- Exam- Exam- Exam- ple 26 ple 27 ple 28 ple 29 ple 30 Organic polymer resin PES PES PES PES PES Water-soluble polymer Inorganic ion adsorbent Sul- Sul- Sul- Sul- Sul- raw material fate fate fate fate fate Inorganic ion adsorbent C C C C C Replacement rate with ethanol 95 95 95 95 95 in inorganic ion adsorbent (% by mass) Supported amount of inorganic 50 50 50 50 50 ion adsorbent (% by mass) Sum total of pore volumes per 0.33 0.35 0.35 0.36 0.35 unit mass of inorganic ion adsorbent measured by nitrogen gas adsorption method (cm.sup.3/g) Pulverization method of Jet Jet Jet Jet Jet inorganic ion exchanger mill mill mill mill mill Average particle diameter of 1.03 1.03 1.03 1.03 1.03 inorganic ion adsorbent (m) Ratio of (maximum particle 67 67 67 67 67 diameter)/(minimum particle diameter) of inorganic ion adsorbent Viscosity of stock liquid 1528 1509 2132 2773 1505 (mPa .Math. s) Granulation by rotating Possi- Possi- Possi- Possi- Possi- nozzle method ble ble ble ble ble Solidification tank 80 80 60 60 60 temperature ( C.) NMP concentration in 50 60 50 50 0 solidification tank (% by mass) Concentration of surfactant 0 0 0 0 0 added to solidification tank (mg/L) Nozzle diameter (mm) 4 4 4 4 4 Average particle diameter 540 538 536 549 548 of porous shaped body (m) Pore volume of porous shaped 0.17 0.18 0.18 0.18 0.18 body measured by nitrogen gas adsorption method (cm.sup.3/g) Specific surface area of 209 197 175 184 190 porous shaped body measured by nitrogen gas adsorption method (m.sup.2/g) Flatness ratio of porous 0.24 0.27 0.09 0.06 0.25 shaped body Bulk density of porous 0.32 0.34 0.36 0.41 0.34 shaped body (g/mL-porous shaped body) Pore volume measured by 1.28 1.22 0.59 0.50 1.25 mercury intrusion method (cm.sup.3/g) Modal pore diameter measured 0.37 0.45 0.14 0.12 0.13 by mercury intrusion method (m) Elastic modulus of porous 3768 3522 4460 4871 3034 shaped body (mN/m.sup.2) Abrasion rate of porous 0.00 0.00 0.17 0.19 0.00 shaped body (% by mass) Sodium hydroxide 0.4 0.4 0.4 0.4 0.4 concentration at the time of washing (% by mass) Sodium hydroxide feed 10 10 10 10 10 amount at the time of washing (times) Sodium hydroxide flow rate 10 10 10 10 10 at the time of washing (h.sup.1) Pure water feed amount at 300 300 300 300 300 the time of washing (times) Pure water feed rate at the 80 80 80 80 80 time of washing (h.sup.1) Leached anion concentration 0.1 0.0 0.7 0.4 0.2 (mg/L) UV absorbance 0.00 0.00 0.07 0.04 0.00 Leached metal ion <0.0001 <0.0001 0.0070 0.0068 <0.0001 concentration (mg/L) pH 6.1 6.1 6.3 6.4 6.8 pH change amount 0.2 0.3 0.3 0.5 0.8 Pressure loss at LV 20 40 45 20 19 39 m/hr (kPa/m) Phosphorus adsorption amount 3.09 3.46 3.52 3.67 2.89 (g-P/L- porous shaped body), SV120 h.sup.1 Phosphorus adsorption amount 3.49 3.91 3.86 3.97 3.25 (g-P/L- porous shaped body), SV240 h.sup.1 Exam- Exam- Exam- Exam- Exam- ple 31 ple 32 ple 33 ple 34 ple 35 Organic polymer resin PES PES PES PES PES Water-soluble polymer Inorganic ion adsorbent Sul- Sul- Sul- Sul- Sul- raw material fate fate fate fate fate Inorganic ion adsorbent C C C C C Replacement rate with ethanol 95 95 95 95 95 in inorganic ion adsorbent (% by mass) Supported amount of inorganic 50 79 79 79 79 ion adsorbent (% by mass) Sum total of pore volumes per 0.34 0.35 0.37 0.35 0.35 unit mass of inorganic ion adsorbent measured by nitrogen gas adsorption method (cm.sup.3/g) Pulverization method of Jet Jet Jet Jet Ball inorganic ion exchanger mill mill mill mill mill Average particle diameter of 1.03 3.40 6.33 0.30 3.51 inorganic ion adsorbent (m) Ratio of (maximum particle 67 265 439 50 295 diameter)/(minimum particle diameter) of inorganic ion adsorbent Viscosity of stock liquid 1558 1463 978 5680 1234 (mPa .Math. s) Granulation by rotating Possi- Possi- Possi- Possi- Possi- nozzle method ble ble ble ble ble Solidification tank 25 60 60 60 60 temperature ( C.) NMP concentration in 0 50 50 50 50 solidification tank (% by mass) Concentration of surfactant 0 0 0 0 0 added to solidification tank (mg/L) Nozzle diameter (mm) 4 4 4 4 4 Average particle diameter of 547 539 535 548 545 porous shaped body (m) Pore volume of porous shaped 0.17 0.28 0.29 0.28 0.28 body measured by nitrogen gas adsorption method (cm.sup.3/g) Specific surface area of 182 224 221 216 220 porous shaped body measured by nitrogen gas adsorption method (m.sup.2/g) Flatness ratio of porous 0.20 0.27 0.39 0.01 0.23 shaped body Bulk density of porous shaped 0.33 0.50 0.51 0.49 0.50 body (g/mL-porous shaped body) Pore volume measured by 1.30 1.03 1.06 1.05 1.05 mercury intrusion method (cm.sup.3/g) Modal pore diameter measured 0.10 0.14 0.14 0.15 0.17 by mercury intrusion method (m) Elastic modulus of porous 3708 6872 6171 6270 6713 shaped body (mN/m.sup.2) Abrasion rate of porous 0.00 0.01 0.02 0.03 0.02 shaped body (% by mass) Sodium hydroxide 0.4 0.4 0.4 0.4 0.4 concentration at the time of washing (% by mass) Sodium hydroxide feed amount 10 10 10 10 10 at the time of washing (times) Sodium hydroxide flow rate at 10 10 10 10 10 the time of washing (h.sup.1) Pure water feed amount at the 300 300 300 300 300 time of washing (times) Pure water feed rate at the 80 80 80 80 80 time of washing (h.sup.1) Leached anion concentration 0.3 0.0 0.1 0.2 0.1 (mg/L) UV absorbance 0.00 0.00 0.00 0.02 0.00 Leached metal ion <0.0001 <0.0001 <0.0001 0.0008 <0.0001 concentration (mg/L) pH 6.7 6.3 6.4 6.8 6.5 pH change amount 0.8 0.5 0.4 0.8 0.7 Pressure loss at LV 20 40 41 52 15 33 m/hr (kPa/m) Phosphorus adsorption amount 2.64 3.23 2.97 3.98 3.15 (g-P/L- porous shaped body), SV120 h.sup.1 Phosphorus adsorption amount 2.96 3.65 3.33 4.38 3.61 (g-P/L- porous shaped body), SV240 h.sup.1 Exam- Exam- Exam- Exam- Exam- ple 36 ple 37 ple 38 ple 39 ple 40 Organic polymer resin PES PES PES PES PES Water-soluble polymer Inorganic ion adsorbent Sul- Sul- Sul- Sul- Chlo- raw material fate fate fate fate ride Inorganic ion adsorbent C C C C C Replacement rate with ethanol 95 95 95 95 95 in inorganic ion adsorbent (% by mass) Supported amount of inorganic 79 79 79 79 79 ion adsorbent (% by mass) Sum total of pore volumes per 0.36 0.34 0.34 0.34 0.32 unit mass of inorganic ion adsorbent measured by nitrogen gas adsorption method (cm.sup.3/g) Pulverization method of Mor- Ball Jet Jet Jet inorganic ion exchanger tar mill mill mill mill Average particle diameter of 32.5 20.0 1.03 1.03 1.03 inorganic ion adsorbent (m) Ratio of (maximum particle 387 513 67 67 67 diameter)/(minimum particle diameter) of inorganic ion adsorbent Viscosity of stock liquid 350 499 2228 2210 2160 (mPa .Math. s) Granulation by rotating Possi- Possi- Possi- Possi- Possi- nozzle method ble ble ble ble ble Solidification tank 60 60 60 60 60 temperature ( C.) NMP concentration in 50 50 50 50 50 solidification tank (% by mass) Concentration of surfactant 0 0 0 0 0 added to solidification tank (mg/L) Nozzle diameter (mm) 4 4 4 4 4 Average particle diameter of 540 545 545 545 542 porous shaped body (m) Pore volume of porous shaped 0.28 0.27 0.27 0.27 0.25 body measured by nitrogen gas adsorption method (cm.sup.3/g) Specific surface area of 224 224 224 224 216 porous shaped body measured by nitrogen gas adsorption method (m.sup.2/g) Flatness ratio of porous 0.55 0.45 0.18 0.16 0.11 shaped body Bulk density of porous shaped 0.47 0.49 0.51 0.51 0.49 body (g/mL-porous shaped body) Pore volume measured by 1.09 1.12 1.02 1.00 1.06 mercury intrusion method (cm.sup.3/g) Modal pore diameter measured 0.18 0.19 0.16 0.18 0.16 by mercury intrusion method (m) Elastic modulus of porous 6080 6805 6912 6124 6660 shaped body (mN/m.sup.2) Abrasion rate of porous 0.01 0.01 0.02 0.02 0.01 shaped body (% by mass) Sodium hydroxide 0.4 0.4 1.0 0.1 0.4 concentration at the time of washing (% by mass) Sodium hydroxide feed amount 10 10 10 10 10 at the time of washing (times) Sodium hydroxide flow rate at 10 10 10 10 10 the time of washing (h.sup.1) Pure water feed amount at the 300 300 300 300 300 time of washing (times) Pure water feed rate at the 80 80 80 80 80 time of washing (h.sup.1) Leached anion concentration 0.0 0.0 0.0 1.4 0.5 (mg/L) UV absorbance 0.00 0.00 0.00 0.15 0.02 Leached metal ion <0.0001 <0.0001 <0.0001 0.0014 0.0020 concentration (mg/L) pH 6.1 6.7 6.3 5.3 5.7 pH change amount 0.2 0.8 0.4 0.5 0.1 Pressure loss at LV 20 61 66 26 24 20 m/hr (kPa/m) Phosphorus adsorption amount 1.80 1.86 3.71 3.79 3.55 (g-P/L- porous shaped body), SV120 h.sup.1 Phosphorus adsorption amount 1.92 2.01 4.39 4.21 4.00 (g-P/L- porous shaped body), SV240 h.sup.1 Compar- Compar- Compar- Compar- Compar- Compar- Compar- ative ative ative ative ative ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 41 ple 42 ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 Organic polymer resin PES PES PES PES PES PES PES PES PES Water-soluble polymer Inorganic ion adsorbent Sul- Sul- Sul- Sul- Sul- Sul- Sul- Sul- raw material fate fate fate fate fate fate fate fate Inorganic ion adsorbent C C C C C C C C Replacement rate with ethanol 95 95 14 0 0 95 95 14 in inorganic ion adsorbent (% by mass) Supported amount of inorganic 79 79 79 79 93 0 79 ion adsorbent (% by mass) Sum total of pore volumes per 0.34 0.34 0.02 0.01 0.01 0.02 unit mass of inorganic ion adsorbent measured by nitrogen gas adsorption method (cm.sup.3/g) Pulverization method of Jet Jet Jet Jet Jet Jet Jet Jet inorganic ion exchanger mill mill mill mill mill mill mill mill Average particle diameter of 1.03 1.03 1.01 1.00 1.00 0.06 0.05 1.01 inorganic ion adsorbent (m) Ratio of (maximum particle 67 67 107 107 107 125 1087 107 diameter)/(minimum particle diameter) of inorganic ion adsorbent Viscosity of stock liquid 2046 2088 2040 1823 3562 624 35000 200000 2009 (mPa .Math. s) Granulation by rotating Possi- Possi- Possi- Possi- Possi- Possi- Impos- Impos- Possi- nozzle method ble ble ble ble ble ble sible sible ble Solidification tank 60 60 60 60 60 60 60 60 60 temperature ( C.) NMP concentration in 50 50 50 50 50 50 50 50 50 solidification tank (% by mass) Concentration of surfactant 0 0 0 0 0 0 0 0 0 added to solidification tank (mg/L) Nozzle diameter (mm) 4 4 4 4 4 4 4 4 4 Average particle diameter of 545 545 540 541 537 540 540 porous shaped body (m) Pore volume of porous shaped 0.27 0.27 0.01 0.01 0.01 0.01 0.01 body measured by nitrogen gas adsorption method (cm.sup.3/g) Specific surface area of 224 224 49 37 44 15 49 porous shaped body measured by nitrogen gas adsorption method (m.sup.2/g) Flatness ratio of porous 0.10 0.15 0.13 0.15 0.02 0.25 0.16 shaped body Bulk density of porous shaped 0.51 0.51 0.47 0.49 0.67 0.21 0.47 body (g/mL-porous shaped body) Pore volume measured by 1.07 1.03 0.81 0.72 0.58 1.42 0.81 mercury intrusion method (cm.sup.3/g) Modal pore diameter measured 0.19 0.18 0.15 0.14 0.14 0.17 0.15 by mercury intrusion method (m) Elastic modulus of porous 6123 6908 7037 6912 11200 981 5225 shaped body (mN/m.sup.2) Abrasion rate of porous 0.00 0.01 0.15 0.16 0.22 0.00 0.15 shaped body (% by mass) Sodium hydroxide 0.4 0.4 0.4 0.4 concentration at the time of washing (% by mass) Sodium hydroxide feed 10 10 10 10 amount at the time of washing (times) Sodium hydroxide flow rate 10 10 10 10 at the time of washing (h.sup.1) Pure water feed amount at 300 300 300 300 300 300 the time of washing (times) Pure water feed rate at the 80 80 80 80 80 80 time of washing (h.sup.1) Leached anion concentration 3.0 7.6 0.5 0.7 0.9 0.1 3.4 (mg/L) UV absorbance 0.44 0.98 0.06 0.09 0.13 0.00 0.48 Leached metal ion 4.1 10 0.0087 0.010 0.021 <0.0001 7.0 concentration (mg/L) pH 4.3 4.0 6.5 6.1 5.9 6.3 4.2 pH change amount 1.6 1.7 0.5 0.2 0.0 0.2 1.6 Pressure loss at LV 20 21 27 28 22 18 40 42 m/hr (kPa/m) Phosphorus adsorption amount 3.75 3.81 1.52 1.31 1.54 0.00 1.58 (g-P/L- porous shaped body), SV120 h.sup.1 Phosphorus adsorption amount 4.25 4.30 1.73 1.44 1.79 0.00 1.71 (g-P/L- porous shaped body), SV240 h.sup.1 C: Hydrated cerium oxide

(96) From the results shown in Table 1 above, it has become clear that, as the replacement rate with an organic liquid becomes higher when an inorganic ion adsorbent is dried, the pore volume of a porous shaped body becomes larger, and a porous shaped body capable of adsorbing a large amount of phosphorus at an ultrahigh water flow rate (SV 120 hr.sup.1, or SV 240 hr.sup.1) can be obtained.

INDUSTRIAL APPLICABILITY

(97) Since a porous shaped body according to the present invention can remove ions, particularly phosphate ions, in water to be treated even at an ultrahigh flow rate of SV 120 hr.sup.1, or SV 240 hr.sup.1, and has a large adsorption capacity, it is particularly suitable for removing a harmful substance in metal coating, pharmaceutical production, medical use, etc.