JPS60132644A - Adsorbent and its preparation - Google Patents

Abstract

PURPOSE:To obtain an adsorbent having phosphorus removing capacity and calcium removal suppressing capacity, by adding and depositing an amorphous zirconium compound and calcium carbonate and/or calcium oxide to spherical activated carbon. CONSTITUTION:1-10wt% of an amorphous zirconium compound (in terms of ZrO2) and 0.05-10wt% of calcium carbonate and/or calcium oxide (as CaCO3) are added and deposited to spherical activated carbon obtained from petroleum or coal pitch and/or org. polymers. Thus obtained adsorbent has phosphorus removing capacity while holding org. substance removing capacity and is suppressed in calcium removing capacity.

Description

Detailed Description of the Invention The present invention provides an adsorbent in which an amorphous zirconium compound and calcium carbonate and/or calcium oxide are impregnated on spherical activated carbon obtained from petroleum-based or coal-based pitch and/or organic synthetic polymers. and its manufacturing method ◎ More specifically, an amorphous zirconium compound is added to spherical activated carbon obtained from petroleum-based or coal-based pitch and/or organic synthetic polymers in an amount of 1 to 1 in terms of ZrO2, and calcium carbonate and/or Calcium oxide is 0.0 in terms of CaCO3.
A water-soluble zirconium compound is added to the spherical activated carbon by immersing the impregnated adsorbent in an amount of 05 to 10 weight, and spherical activated carbon obtained from petroleum-based or coal-based pitch and/or organic synthetic polymers in an aqueous solution of a water-soluble zirconium compound. After complete impregnation, alkali treatment and water washing at 400-1000℃
The resulting amorphous zirconium compound-impregnated spherical activated carbon is immersed in an aqueous solution of a calcium compound to impregnate the amorphous zirconium compound-impregnated spherical activated carbon with a calcium compound, washed with water, dried, and then heated with nitrogen gas and/or carbonic acid. The present invention relates to a method for producing an adsorbent comprising heat treatment at a temperature of 400 to 700°C in a gas atmosphere.

Currently, in patients with impaired renal function (or liver function), waste products and toxic substances (in vivo decomposition and in vitro excretion) are insufficient.
These accumulate in the body and cause various physiological disorders.

The number of patients with such renal (liver) disorders is increasing year by year, and there is therefore a strong need for the development of a method for removing these waste products and poisons from living organisms.

Hemodialysis is the most widely used and popular method for patients with chronic renal failure. Furthermore, research is underway to improve treatment methods, such as by using activated carbon in combination with blood adsorption. On the other hand, it is well known that hyperphosphatemia occurs due to impaired phosphorus excretion in patients with chronic renal failure, and hyperphosphatemia is completely eliminated not only in patients in the conservative stage (before hemodialysis) but also during dialysis. cannot be prevented.

Activated carbon has excellent ability to remove organic metabolites such as creatinine, and is extremely useful as a blood adsorbent.
The ability to remove minerals such as phosphorus is extremely low, and no effect on improving hyperphosphatemia can be expected. Therefore, there is a strong demand for an adsorbent that has the ability to remove phosphorus while retaining the organic matter adsorption ability of activated carbon. One such type of activated carbon is one in which an amorphous zirconium compound is impregnated into the pores of a specific activated carbon.However, in this case, although it shows good adsorption power for organic matter and phosphorus, It also exhibits a certain degree of adsorption ability for calcium ions, potentially causing hypocalcemia, so some kind of solution was needed. Therefore, while retaining the full organic matter removal ability of activated carbon,
There is a strong need for the development of an adsorbent that has phosphorus removal ability and has a refreshingly suppressed calcium removal ability.

The adsorbent of the present invention contains an amorphous zirconium compound and calcium carbonate and/or calcium oxide in the pores of spherical activated carbon, and has properties not found in conventional adsorbents.

The spherical activated carbon used in the present invention is preferably produced from pitches and/or organic synthetic polymers.

The spherical activated carbon according to the present invention is disclosed in Japanese Patent Publication No. 50-18879 2.
%Kaisei 56-69214 2%Kaisei 54-105897
It can be produced by the manufacturing method disclosed in No. In addition, as raw organic synthetic polymers, thermosetting resins such as phenol resins and epoxy resins, or thermoplastic resins such as styrene resins, vinylidene chloride resins, and copolymer resins thereof can be used, and conventionally known methods can be used. can be used to produce spherical activated carbon that can be used in the present invention. The activated carbon used in the present invention has a spherical shape in terms of durability and shape retention, a diameter of 0.05 to 3 mm, and a specific surface area of 500 to 20 mm.
Spherical activated carbon having the characteristics of 0.00 m"/I, cumulative pore volume of 0.1-1.3 cm"/11 with a radius of 10-75000X is preferred.

The amorphous zirconium compound, which is one of the substances attached to the spherical activated carbon in the present invention, does not show any diffraction lines indicating crystallinity in the plug angle 2θ range of 10 to 60° when measured by X-ray diffraction. For example, as shown in figure flK4, there is no reflection spectrum indicating crystals for 20.

As the water-soluble zirconium compound to be attached to the spherical activated carbon, a halogenated zirconium compound or a zirconium oxyacid salt is used. As the halogenated zirconium compound, ZrCl2. ZrBr2rZrC15rZrBr5
+ ZrCl4. ZrBr4+ ZrI4+ Zr0
Ct2'8H20, etc., and Zr(No5)4'5H20, Zr0(No,
)2・2H20,Zr(SO2)2゜Zr (804)
2.4 H20, Z ro (Soa), etc.

The attitude of the aqueous solution of the water-soluble zirconium compound used when impregnating the spherical activated carbon with the water-soluble zirconium compound is 3 to 60. i quantity chi.

After impregnating spherical activated carbon with a water-soluble zirconium compound, it is treated with alkali, and the alkalis used in this case include ammonia aqueous solution, KOH aqueous solution, and NaOH.
There are aqueous solutions and ammonia gas, etc.

Particularly preferred are aqueous ammonia solution and ammonia gas.

The alkali treatment is involved in making the water-soluble zirconium compound impregnated into the spherical activated carbon amorphous and metathesizing the halogenated zirconium compound or tj:sil:I=rum oxyacid into water-soluble salts.

After alkali treatment, wash with water,
The heat treatment is carried out at a temperature of preferably 800 to 100°C. If the temperature is below 400°C, there will be a problem with residual alkali such as an ammonia odor, and if the temperature is above 1000°C, the adsorption performance will not be strong and it will be economically disadvantageous, so the treatment temperature should be 400°C. ~1000°C is preferred.

In the adsorbent of the present invention, the amorphous JX zirconium compound is ZrO
It is preferable that 1 to 10% by weight is attached in terms of □.

If the amount of impregnated amorphous zirconium compound is less than 1% by weight, the effect of adsorption on phosphorus is small, and if it is more than 10% by weight, it becomes difficult to impregnate the amorphous zirconium compound.
Moreover, the rate of increase in the amount of impregnation does not significantly improve the phosphorus adsorption rate.

Calcium carbonate and/or calcium oxide, which is the other substance attached to the spherical activated carbon in the present invention, is
Spherical activated carbon impregnated with amorphous zirconium compound Spherical activated carbon impregnated with amorphous zirconium compound impregnated with a calcium compound After immersing in a calcium compound and completely washing with water and drying,
The amorphous zirconium compound is impregnated onto the spherical activated carbon by heating it to a temperature of 400 to 700° C. in a nitrogen and/or carbon dioxide atmosphere.

As the calcium compound impregnated into the spherical activated carbon impregnated with an amorphous zirconium compound, an inorganic calcium compound or an organic calcium compound is used.

As an inorganic calcium compound, cact2. ca(No
)2°ca (czos)2. CaI2+ Ca520
5. Ca52061Ca(SO2NH2)21 Ca
5041 CaS+ and Ca(OH)z anhydrous salts and their hydrated salts, organic calcium compounds include calcium acetate, calcium lactate, calcium malate,
Examples include calcium glycerophosphate, calcium D-gluconate, calcium salicylate, and hydrates thereof.

The concentration of the calcium water bath solution impregnated into the spherical activated carbon impregnated with the amorphous zirconium compound is 0.05 to 4ON.

After impregnating spherical activated carbon impregnated with an amorphous zirconium compound with an aqueous solution of a calcium compound, the activated carbon is washed with water, dried, and heat-treated at 400-700°C, preferably 600-700°C.

In the adsorbent of the present invention, it is preferable that calcium carbonate and/or calcium oxide be impregnated on spherical activated carbon impregnated with a weightless zirconium compound of 0.05 to 10 weight percent in terms of CaCO5.

A preferred method for impregnating calcium carbonate and/or calcium oxide on the amorphous zirconium compound-impregnated spherical carbon includes the following method.

(1) The resulting amorphous zirconium compound-impregnated spherical activated carbon f is immersed in a CaCt2 aqueous solution to impregnate the amorphous zirconium compound-impregnated spherical activated carbon with CaC12f, washed with water,
After drying, it was immersed in an aqueous solution of carbonate such as (NH4)2COs, washed with water, dried, and further heated for 400 min in a carbon dioxide atmosphere so that chlorine ions or sulfate ions could be easily removed by subsequent heat treatment. A method of impregnating calcium carbonate and/or calcium oxide on spherical activated carbon impregnated with an amorphous zirconium compound by heat treatment at ~700°C.

(2) The resulting amorphous zirconium compound-impregnated spherical activated carbon f is immersed in a Ca(OH)z aqueous solution to completely impregnate the amorphous zirconium compound-impregnated spherical activated carbon with Ca(OH)2, and then washed with water and dried. 400-7 under carbon dioxide atmosphere
A method of impregnating calcium carbonate and/or calcium oxide on spherical activated carbon impregnated with an amorphous zirconium compound by heat treatment at 00°C.

(3) Calcium lactate♂,? 4. Crushed and impregnated with calcium lactate, washed with water and dried, then crushed under nitrogen gas atmosphere to 400~7
A method of impregnating calcium carbonate and/or calcium oxide on spherical activated carbon impregnated with an amorphous zirconium compound by heat treatment at 00°C.

The adsorbent of the present invention is one in which an amorphous zirconium compound and calcium carbonate and/or calcium oxide are impregnated with spherical activated carbon produced from pitches and/or organic synthetic polymers, This is completely different from conventional adsorbents made by granulating zolconium oxide hydrate. The adsorbent of the present invention has the ability to completely adsorb phosphorus components such as phosphate ions, suppresses the adsorption of calcium components in serum, and has the adsorption properties of activated carbon, such as iodine, creatinine, VB, It has the ability to absorb dog lint and decolorize caramel. In other words, it is useful for the treatment of hyperphosphatemia by adsorbing phosphorus components, and it also prevents hypocalcemia that occurs during the treatment of hyperphosphatemia by suppressing the adsorption of calcium components. It is useful as an adsorbent for artificial organs.

In addition, the adsorbent of the present invention can be used by coating it with a polymer such as gelatin, alzomine, polyHEMA, or the like. It can also be used in combination with other adsorbents or in combination with other dialysis methods such as filtration. In addition, it can also be used as an oral adsorbent for the purpose of orally administering and removing phosphorus in the gastrointestinal tract.6 The present invention will be described in detail below based on activated carbon production examples and examples.

Activated carbon production example 1 Pitch obtained by petroleum pyrolysis (softening point 190°C,
Quinoline solubility 30% by weight, H/C element f, ratio 0.6
) 300 M negative part K, 1 ook part of naphthalene,
Adding 2 weight more polyethylene to the pitch,
Put this in a 1 liter autoclave, mix, and heat to 180°C.
The mixture was mixed and melted at a temperature of 2 hours with stirring. By pouring the pitch mixture melt into heated water containing 0.5% by weight polyvinyl alcohol, which had been preheated to 160°C, and dispersing it at 1200 rpm for 20 minutes,
Pitch mixture spheres with an average particle size of 850 μm were obtained by spheroidization and subsequent cooling of the whole. Next, after dehydration, naphthalene was extracted and removed using n-hexane, and the mixture was transferred to a fluidized bed with air passed through it, and heated at 30°C/hr from room temperature.
The temperature was raised to 300°C under the following conditions to obtain infusible pitch spherical gold. Subsequently, 100 g of infusible pitch spheres were carbonized at a temperature of 900° C. in steam, and further maintained at a temperature of 900° C. for 2 hours to obtain activated spherical activated carbon.

The average particle size of the obtained spherical activated carbon was 800 μm, the specific surface area was 1100 m”/Ji′, and the radius lo ~ 750
The cumulative pore volume of 00X is 1.0 cm"/'-c6,
Activated carbon production example 2 Pi, thea 50 with a softening point of 182°C, quinolinous soluble content of 10% by weight, and a H/C base ratio of 0°53.
The weight part of Natsutarif 250 heavy prize part was introduced into a pressure-resistant container equipped with a stirring blade, mixed and melted by heating at 210°C, and 80 to 9
It was cooled to 0°C and adjusted to a viscosity suitable for extrusion spinning, and the diameter was 1.
50k from the cap at the bottom of the container with 10 0mm holes
g/cm'' pressure: 5001//
It was extruded at a rate of min.

The extruded string-like pitch was flowed into a cooling tank at a temperature of 10 to 25° C. along a full-layer glass trough with an inclination of about 40°. The string-like pitch immediately after extrusion was continuously stretched by flowing water down the gutter at a flow rate of 3.0 m/sec.

String-like pitches with a diameter of 500 μm were accumulated in the cooling tank. By leaving it in water for about 1 minute, the string-like pitch solidified and was easily broken by hand. This string-like pitch was placed in a high-speed cutter, water was added, and cutting was carried out for 10 to 30 seconds to complete the crushing of the string-like pitch and become rod-like pitch.

When observed under a microscope, the average length to diameter ratio of a cylinder is 1.5.
Met.

Next, this rod-shaped pitch eF was separated and heated to 90°C.
10M parts of the rods were put into 100 parts by weight of an aqueous solution of % polyvinyl alcohol, melted, dispersed with stirring, and cooled to form a slurry of spherical pitch.

The average particle size of the spherical pitch beads was 850 μm. Extraction was performed using the obtained beads fn-hexane to extract naphthalene in the pitch beads. Next, all oxidative infusibility was carried out using air in a fluidized bed.

The conditions for infusibility are 20 n/m for 100 I beads.
In air is sent to 300°C under the temperature increase condition of 30°C/hr.
All oxidation and infusibility was carried out.

Infusible beads 1001k, heated to 900°C at 200°C/hr in a fluidized bed with a steam atmosphere containing N2 gas.
The temperature was raised to 900° C. and maintained at a temperature of 900° C. for 2 hours. The obtained activated carbon was spherical with an average particle size of 800 μm. The produced activated carbon has a specific surface area of 1100 m"/1. and a cumulative pure pore volume of 10 to 75000X radius of 1.0 cm"/1.
I! Met.

Activated carbon production example 3 Polyvinylidene chloride particles (average particle size 900 μm) were heated in a fluidized bed (quartz tube of 50 haφ) from room temperature to 300 μm.
Polycondensation was performed at the same time as dehydrochlorination by flowing nitrogen gas and heating under conditions of 10° C./hr up to 1:1. The heat-treated polymer formed infusible spheres that were infusible by heat. Subsequently, infusible spheres were used in water vapor for 9
Spherical activated carbon (average particle size:
800 μm, specific surface area: 1000 m”/I and radius l
O~75000
cm”/I) 'i get i.

Example 1 [Method for manufacturing spherical activated carbon impregnated with amorphous zirconium compound] Zirconium oxychloride (Z r0C12 8H20)
Dissolve in water to make a Zr0Ct2 aqueous solution 3 with a concentration of 27N
00goft prepared. Next, 100 g of the spherical activated carbon produced in Activated Carbon Production Example 1 was added to 300 rnl of the above 2.7 M% zirconium oxychloride aqueous solution, and the zirconium component was removed over a period of 2 hours using a rotary evaporator with a water bath temperature of 50°C. Impregnated into spherical activated carbon. After impregnating the zirconium component into the spherical activated carbon, the remaining aqueous solution and the obtained spherical activated carbon were separated, and after separating the P, they were poured into 500 Inl of 10% ammonia water, stirred for 2 and a half hours, and then the remaining aqueous solution and the zir, - Spherical activated carbon completely impregnated with a nium compound was distributed door to door.

Next, the spherical activated carbon separated from each house was washed with light and water, and then placed in a nitrogen stream for 2
The temperature was raised to 900°C at a rate of 000/hr and maintained at 900°C for 1 hour. After heat treatment, by cooling the spherical activated carbon, the zirconium compound is reduced to about 8.6% by weight (Z
The attached adsorbent (rO□ conversion) was obtained.

When the obtained zirconium compound-impregnated spherical activated carbon was analyzed by X-ray diffraction, it showed a diffraction mi as shown in FIG. 4, which revealed that the impregnated zirconium compound was amorphous.

Furthermore, in order to investigate the impregnated state of the zirconium compound, the distribution state of zirconium was measured on the cross section of the activated carbon using an X-ray microanalyzer.

FIG. 1 is a cross-sectional photograph of the activated carbon of activated carbon production example 1, and FIG. 2 is a cross-sectional photograph of the adsorbent of this example. In the photograph, the central white line is the X-ray scanning line, and when zirconium is present, fluorescent X-rays originating from zirconium are emitted, and a wavy line spectral peak is shown at the bottom of the drawing. As shown in FIG. 1, the activated carbon of Activated Carbon Production Example 1 does not have a zirconium compound impregnated with it, so there is no wavy line derived from zirconium. On the other hand, as shown in Figure 2, in the adsorbent produced in this example, the spectral line of zirconium has a high average waveform, so zirconium can be uniformly impregnated onto the activated carbon. be discovered.

[Method of impregnating calcium carbonate and/or calcium oxide on spherical activated carbon impregnated with an amorphous zirconium compound]

Amorphous zirconium compound 10% by weight calcium chloride aqueous solution 250II' for 100g of impregnated spherical activated carbon
f: Added and immersed for 3 hours while stirring at room temperature. Next, the calcium chloride aqueous solution and the impregnated carbon were completely separated, and the impregnated carbon was completely washed with 350a of ion-exchanged water and drained, and then the impregnated carbon was dried in a dryer at 110° C. for 12 hours. Furthermore, 5% by weight ammonium carbonate aqueous solution '130
0.9 was added and the reaction was stirred for 3 hours. After the reaction, the painted charcoal and ammonium carbonate aqueous solution were separated, drained, and the impregnated charcoal was washed with 350°C of ion-exchanged water, and then heated at 110°C for 12 hours.
Drying was carried out for a period of time. The dried charcoal was heat-treated in a carbon dioxide atmosphere at 700°C to obtain 1011I calcined impregnated charcoal. A diffraction peak as shown in FIG. 7 of the XifM diffraction spectrum was obtained from the calcium supported on the impregnated carbon. This diffraction peak is the 6th peak of calcium carbonate (CaC03) in Figure 5.
Identification from the peak of calcium oxide (Cab) in the figure revealed that the compatible calcium was CaCO5 and CaO. From this, it was confirmed that the calcium impregnated onto the amorphous zorconium and activated carbon by the above method consisted of calcium carbonate and/or calcium oxide.

In order to investigate the state of impregnation of lucium compounds, the entire cross-section of the impregnated carbon was measured using an X-ray microanalyzer similar to that used to confirm zolconium compounds, and the results shown in Figure 3 were obtained. As shown in the figure, spectral peaks of fluorescent X-rays originating from the calcium element were detected in the center and periphery of the impregnated carbon, indicating that calcium was impregnated with the activated carbon.

As a result of treating the impregnated carbon with dilute hydrochloric acid and measuring dissolved calcium by atomic absorption spectrometry, it was confirmed that calcium was present in an amount of 1.0% by weight in terms of Ca and CO5.

Example 2 Using the spherical activated carbon impregnated with an amorphous zirconium compound obtained by the method for producing spherical activated carbon impregnated with an amorphous zirconium compound of Example 1, the same procedure as that of Example 1 was carried out except that the spherical activated carbon impregnated with an amorphous zirconium compound was immersed in a 20 wt. Under similar operating conditions, the amorphous zirconium compound was 8.6% by weight (Zr0z equivalent) and the calcium carbonate and/or calcium oxide was 3.0% by weight.
An adsorbent impregnated with weight% (calculated as Ca COs) was obtained.

Example 3 Using the amorphous zirconium compound-detachable activated carbon obtained by the method for producing amorphous zirconium compound-impregnated spherical activated carbon of Example 1, Example 1 was performed except that it was immersed in an aqueous solution of 30% by weight of calcium chloride. Under the same operating conditions as above, 8.6% by weight of amorphous zirconium (calculated as ZrO2), 5.0% by weight of calcium carbonate and/or calcium oxide (Ca
(CO5 equivalent) was obtained.

Example 4 0.1% by weight based on 100.9% of the amorphous zirconium compound impregnated spherical activated carbon obtained by the method of spinning the amorphous 7J11' zirconium compound spherical activated carbon of Example 1
300g of gold was added to the aqueous solution of commercially available calcium, and the mixture was immersed for 3 hours at room temperature with stirring.

Next, the calcium hydroxide aqueous solution and the impregnated carbon were separated, and the impregnated carbon was washed with 350 ml of ion-exchanged water. Further, this water-washed impregnated carbon was dried in a drying oven at 110° C. for 12 hours.

Next, dry impregnated charcoal? After heat treatment in a carbon dioxide atmosphere at near 00℃, the amorphous zirconium compound was 8.6% by weight (
About 100% of adsorbent was obtained, to which 0.5% by weight (calculated as CaCO3) of calcium carbonate and calcium oxide was impregnated.

As shown in FIG. 8, it was confirmed from the X-ray diffraction spectrum that the coexisting calcium was deposited as CaCOs.

Example 5 1.0 weight of calcium lactate aqueous solution 3001 was added to 100 g of the amorphous zirconium compound-impregnated spherical activated carbon obtained by the method of manufacturing the amorphous zirconium compound-impregnated spherical activated carbon of Example 1, and the mixture was heated at room temperature. While stirring 3
Impregnated for hours. Next, the calcium lactate aqueous solution and the impregnated carbon were separated, and the impregnated carbon was washed with 350 d of ion-exchanged water. This water-washed impregnated carbon was dried in a drying oven at 110° C. for 12 hours.

Next, the dried impregnated carbon was heat-treated in a N2 gas atmosphere at 700°C, and the amorphous zirconium compound was 8.6% by weight (
About 100 y of adsorbed carbon was obtained, on which 0.5% (in terms of CaCO5) of calcium carbonate and calcium oxide was impregnated.

As shown in FIG. 9, it was confirmed from the X-ray diffraction spectrum that the covalent calcium was attached as CaCO3.

Example 6 The spherical activated carbon obtained in Activated Carbon Production Example 2 was used to produce an amorphous zirconium compound of 8. A spherical activated carbon impregnated with an amorphous zirconium compound in an amount of 6% by weight (calculated as ZrOz) was obtained.

Next, the obtained spherical activated carbon impregnated with an amorphous zirconium compound is subjected to the same operating conditions as in Example 1, in which calcium carbonate and/or calcium oxide is added to the spherical activated carbon impregnated with an amorphous zirconium compound. Possibly 8.6jl of amorphous norconium compound (% by weight (ZrOz exchanged
．． Spherical activated carbon impregnated with 0% by weight (calculated as CaCO3) was obtained.

From the Xj1M diffraction spectrum of the impregnated spherical activated carbon, it was confirmed that the coexisting calcium was calcium carbonate and calcium oxide, as in FIG. 7 of Example 1.

fruit! i! Example 7 Using the spherical activated carbon obtained in Activated Carbon Production Example 3, the process was carried out under the same operating conditions as in Example 1 for producing spherical activated carbon impregnated with an amorphous zirconium compound (non-crystalline activated carbon). Crystalline zirconium compound is 8.6
Weight % (calculated as Zr0□)) was obtained.

Next, using the obtained amorphous zirconium compound-impregnated spherical activated carbon, the same operating conditions as in the method of impregnating calcium carbonate and/or calcium oxide to the amorphous zirconium compound-impregnated spherical activated carbon described in Example 1 were carried out. By implementing the method, the amount of amorphous zirconium compound 8.6N% (Z
An adsorbent was obtained in which 1.0% by weight of calcium carbonate and/or calcium oxide (calculated as CaCO5) was attached.

Example 8 Using the spherical activated carbon obtained in activated carbon production example 1, Example 10
By carrying out the method for producing amorphous zirconium compound-impregnated spherical activated carbon under the same operating conditions except that the total concentration of the zirconium oxychloride water bath solution was 19% by weight,
Amorphous zirconium compound 6.5i mass % (ZrO2 equivalent and calcium carbonate and/or calcium oxide 1.0
Weight % (Ca co.

(conversion) All of the impregnated spherical activated carbon was obtained. From the XN diffraction spectrum of this impregnated spherical activated carbon, it was confirmed that the supported calcium was calcium carbonate and calcium oxide similar to those shown in FIG. 7 of Example 1.

Example 9 The spherical activated carbon obtained in Activated Carbon Production Example J was used, and the same operating conditions as in the method for producing spherical activated carbon impregnated with an amorphous zirconium compound of Example 1 were carried out except that the concentration of the zirconium oxychloride water bath solution was changed to 11% by weight. By carrying out the
The amorphous zirconium compound is 4.0 molten metal (Zr0z conversion) and the calcium carbonate and/or calcium oxide is 1
．． Spherical activated carbon impregnated with 0% by weight (in terms of ChCO3) was obtained.

Example 10 Using the spherical activated carbon obtained in Activated Carbon Production Example 1, the same method as in Example 1 for producing spherical activated carbon impregnated with an amorphous zirconium compound was carried out except that the concentration of the zirconium oxychloride water bath solution was changed to 5% by weight. By performing under operating conditions,
Amorphous zirconium.

1.5% by weight of the compound (calculated as ZrO2) and 1.0% by weight of calcium carbonate and/or calcium oxide (CaC
Obtained spherical activated carbon impregnated (in terms of O5).

In order to clarify the effects of the present invention, an adsorbent manufactured according to the following comparative example was subjected to the tests described below.

Comparative Example 1 Activated spherical activated carbon 'f' was obtained by performing the same operation as in Activated Carbon Production Example 1. The obtained spherical activated carbon has an average particle size of 800 μm, a specific surface area of 1,100 m''/7, and a cumulative pore volume of 75' 1.0 at a diameter of 10 to 75,000.
cm"/l/. A cross-sectional photograph showing the distribution state of zolconium by X-ray microanalyzer on the activated carbon cross section is shown in Figure 1. In the photograph, the central white line is the Xa scanning line, and the zirconium element When zirconium is present, fluorescent X-rays originating from zirconium are emitted, and a spectral peak at the curved part in is shown at the bottom of the curve.As shown in Figure 1, the activated carbon of Production Example 1 is a zirconium compound
fc tA'A The wavy line is small because I didn't look at it.

Comparative Example 2 Same operation treatment as activated carbon production example 1? Using the activated spherical activated carbon obtained in this process, the same operation treatment as in the method for producing spherical activated carbon impregnated with an amorphous zirconium compound in Example 1 was performed to obtain spherical activated carbon impregnated with an amorphous zirconium compound. zirconium compound adsorption activated carbon 4
Analysis by X-ray diffraction showed all diffraction lines as shown in Figure 4, and it was found that the attached zirconium compound was amorphous, while X-ray microanalyzer measurement showed that the zirconium compound was amorphous. From the cross-sectional photograph in the figure, it can be seen that the spectral line of norconium has an average waveform of 'km' and that zirconium is uniformly attached to the activated carbon.

Comparative Example 3 The same method as in Example 1 in which calcium carbonate and/or calcium oxide is impregnated with the amorphous zirconium compound-impregnated activated carbon on activated spherical activated carbon obtained by performing the same operation treatment as in Activated Carbon Production Example 1. Calcium-impregnated spherical activated carbon was obtained by various operations. The calcium supported on the impregnated spherical activated carbon thus obtained was found to be in the form of calcium carbonate, as shown in Figure 10, as determined by X-ray diffraction.
It was f1g.

Regarding the amount of added N, impregnated carbon was treated with hydrochloric acid and the amount of Ca was measured by atomic absorption method. As a result, the amount of impregnated calcium U CaC0
It was confirmed that the inspection was carried out by 1.0% in terms of 3fd.

Test Examples The physical property values and adsorption characteristics of the adsorbents produced in Examples 1 to 10 and Comparative Examples 1 to 3 are shown in the table below. Table 1 shows that the amorphous zirconium compound and the spherical activated carbon impregnated with calcium carbonate and/or calcium oxide of the present invention have the ability to suppress calcium adsorption and at the same time retain phosphorus adsorption properties and other adsorption properties. And Figure 11 "P" is displayed.

The methods for measuring the characteristic values of the present invention and those listed in the table below are as follows: (1) Cumulative pore volume: The pore volume in the range of 10 to 75,000 pore radii is measured and accumulated by the following method.

Methanol adsorption method (
Measuring device manufactured by Nitanaka Scientific Instruments.

AS-703D model), pore radius in the range of 80 to 75,000X is measured using a mercury intrusion porosimeter (measuring device: Carlo Erba, series 2oo model), and the total measurement value is added up to determine the pore radius of 10 to 75,000X. The cumulative pore volume of the radius is determined.

Regarding the measurement of cumulative pore volume and the method of measuring specific surface area described in the next section, please refer to Kohei Urano: "Kimono" Vol. 13, No. 10, 583.
~591 negative and the same volume, No. 12, full volume, pages 738-744 (1
9,75) ■ Detailed information is published by Kojosha.

(Specific surface area: Based on methanol adsorption method.

(3) Amount of calcium impregnated: A sample was treated with dilute hydrochloric acid, and the calcium content in the solution was measured by atomic absorption spectrometry to calculate the content of calcium in the sample.

(4) Amount of zirconium impregnated: Sample 11! In an oxidizing atmosphere 1. The ash content remaining after burning at 900°C for 4 hours in an air furnace was calculated (in terms of ZrO2).

(5) Serum test: Calcium and phosphorus measurements are performed by Chugai Pharmaceutical R.
Creatinine was measured based on the aBA-Mark n method using a Peckman creatinine analysis needle.

Human Ssrum iCNaH2PO4・2H
A test method is used in which serum is added with 2Of to adjust the phosphorus concentration to 10 to 12η/di, and creatinine is added to adjust the creatinine concentration to approximately x0+v/aKM. Add 0.5 l of sample to 10 g of adjusted serum, shake at 37°C for 2 hours,
Collect the supernatant serum and extract calcium and phosphorus.

Measure the concentration of creatinine, etc.

(6) The crystal form of the impregnated calcium and zirconium compounds is determined by the diffraction nof turn of Xm diffraction. (7)
Vitamin B1□ adsorption rate, inulin adsorption rate: initial concentration 100
ppm vitamin horse 2. Inulin phosphate buffer (p
H7,4) (1) Sample r in 100m7! f 11'l
Add Z and shake at 37°C for 3 hours to absorb. After shaking, separate the solution and adsorbent using F paper, define the adsorbate concentration in the solution, and calculate the adsorption rate.

Here, C8 represents the density before adsorption (mf/dx) and C represents the concentration after adsorption <q/at).

[Brief explanation of the drawing]

Figure 1 shows the distribution of syzirconium on the cross section of the spherical activated carbon of activated carbon production example 1 measured with an X-ray microanalyzer. Figure 2 shows the distribution of zirconium on the cross section of the adsorbent of Example 1 measured with the Figure 3 is a photograph of the calcium distribution state taken by an X-ray microanalyzer on the cross section of the adsorbent of Example 1. Figure 4 is an Xi diffraction graph of the zirconium crystal system impregnated with only the zirconium compound of Example. The figure is an X-ray diffraction graph of Ca Co 5, and Figure 6 is a graph of C
X-ray diffraction graph of aO, Figure 7 is an X-ray diffraction graph of the adsorbent impregnated with the zirconium compound and calcium compound of Example-1, and Figure 8 is the X-ray diffraction graph of the adsorbent impregnated with the zirconium compound and calcium compound of Example-4. Figure 9 is the X1M diffraction graph of the adsorbent impregnated with the zolconium compound and calcium compound of Example-5. Figure 10 is the X1M diffraction graph of the adsorbent impregnated with the calcium compound of Comparative Example-3. Line diffraction graph, Figure 11-1 is a graph showing the calcium suppression effect in serum of Examples and Comparative Examples, Figure 11-2 is a graph showing phosphorus adsorption behavior in serum of Examples and Comparative Examples. . Figure 2 Figure 3 Do1

Claims (1)

[Scope of Claims] (Li) Spherical activated carbon obtained from petroleum-based or coal-based pitch and/or organic synthetic polymers contains an amorphous zirconium compound of 1 to 10% by weight in terms of Zr0□ and calcium carbonate and/or Or calcium oxide is 0.0 in terms of CaCO3
Adsorbent impregnated with 5-10% by weight. (2) The diameter of the spherical activated carbon is 0.05 to 3 m, the specific surface area is 500 to 2000 m"/11, and the radius is 1.
Cumulative pore specific volume of 0 to 75000X is 0.1 to 1.3
cm”/I. (3) The amorphous zirconium compound crystallizes at a plug angle of 2θ in the range of 10 to 60 degrees in X-ray diffraction measurement. The adsorbent according to claim 1, characterized in that it does not exhibit any diffraction that indicates its properties. (4) Spherical activated carbon obtained from petroleum-based or coal-based pitch and/or organic synthetic polymers. The spherical activated carbon is impregnated with the water-soluble zirconium compound by immersing it in an aqueous solution of the water-soluble zirconium compound, and then treated with alkali, washed with water, and then heat-treated at 400 to 1000°C to impregnate the resulting amorphous zirconium compound. The spherical activated carbon is immersed in an aqueous solution of a calcium compound to impregnate the amorphous zirconium compound-impregnated spherical activated carbon with the calcium compound, washed with water and dried, and then heated at 400 to 700°C in a nitrogen and/or carbon dioxide atmosphere.
A method for producing an adsorbent, characterized by heat treatment at a temperature of . (5) The water-soluble zirconium compound is ZrCt2゜ZrBr2# ZrCL5r ZrBr, a ZrC
14aZrBr4゜B r I a and ZrOCl2"
A water-soluble zolconium halodane compound selected from the group consisting of 8 H2O or Zr(No5)4"
5H20, Zr0(NH3)2・2H20, zr(s
o4)2. zr(so4)2' 2H20 and zro(
5. The manufacturing method according to claim 4, wherein the water-soluble zirconium oxyacid is selected from the group consisting of SO4). (6) The calcium compound is CaCl21Ca(N
O3)21Ca(C6O3)2. CaI2* Ca52
o5y Ca5206°ca (so4Na2)2. Ca
an inorganic calcium compound selected from the group consisting of SO4+ CaS and Ca(0)1) 2 or the group consisting of calcium acetate, calcium benzoate, calcium lactate, calcium malate, calcium glycerophosphate, calcium D-gluconate, and calcium salicylate VCI! The manufacturing method according to claim 4, which is an IeF-characteristic. (7) The spherical activated carbon impregnated with the amorphous zirconium compound is C
The amorphous zirconium compound-impregnated spherical activated carbon is impregnated with CaCl2 by immersion in an aCt2 aqueous solution, washed with water and dried, then immersed in an aqueous solution of a carbonate such as (NH4)2Co, then washed with water and dried, and further treated with carbon dioxide gas. 40 under atmosphere
The manufacturing method according to claim 4, characterized in that the heat treatment is performed at a temperature of 0 to 700°C. (8) Spherical activated carbon impregnated with the amorphous zirconium compound
-The amorphous zirconium compound-impregnated spherical activated carbon is impregnated with Ca (Oh)2 by immersion in a Ca(OH)z aqueous solution, washed with water and dried, and then heated to 400~
The manufacturing method according to claim 4, characterized in that the heat treatment is performed at a temperature of 700°C. (9) The amorphous zirconium compound-impregnated spherical activated carbon is immersed in a calcium lactate aqueous solution to impregnate the amorphous zirconium compound-impregnated spherical activated carbon with calcium lactate, washed with water, dried, and then heated at a temperature of 400 to 700°C under a nitrogen gas atmosphere. 5. The manufacturing method according to claim 4, wherein the manufacturing method is heat-treated. 5. The manufacturing method according to claim 4, wherein the amorphous zirconium compound is attached in an amount of 1 to 10% by weight in terms of Zro2. (11) The concentration of the zirconium compound in the water-soluble zorconium compound aqueous solution is 3 to 60% by weight.
- The manufacturing method according to claim 4 (2) characterized in that the calcium compound is impregnated in the form of calcium carbonate and I or calcium oxide in an amount of 0.05 to 10% by weight in terms of CaCOs. The manufacturing method according to claim 4. Sakaki The manufacturing method according to claim 4, wherein the concentration of the calcium compound in the calcium compound aqueous solution is 0.05 to 40% by weight. (14) The manufacturing method according to claim 4, wherein the alkaline treatment of the spherical charcoal impregnated with the water-soluble zirconium compound is carried out using an ammonia aqueous solution or ammonia gas.