JPS6259973B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel adsorbent, and more particularly to an adsorbent comprising a microporous oxide composite containing silica and titania, and having particularly excellent adsorption ability for metal ions and various organic substances. Currently, activated sludge methods and coagulation methods are used to remove various harmful substances that are harmful to humans, animals and plants, and are undesirable in terms of environmental conservation, such as heavy metals and various organic substances, from liquids that contain these dissolved substances. However, these methods have drawbacks such as not being reusable and producing secondary environmental pollutants. On the other hand, adsorption methods are said to be most effective for low-concentration contaminated wastewater, and various adsorbents have been studied, but there has been relatively little research on synthetic inorganic adsorbents. Only synthetic zeolites, calcium silicate and hydrous titanium oxide wrapped in acrylamide have been proposed.
However, these conventionally proposed synthetic inorganic adsorbents have drawbacks such as low adsorption capacity, slow adsorption rate, poor selectivity, cannot be regenerated, high manufacturing cost, and complicated handling. It's not satisfying. The inventors of the present invention conducted extensive research in search of a more effective adsorbent, and as a result, found that a microporous composite oxide composed of silica and titania has excellent adsorption properties for metal ions and various organic compounds. The inventors discovered that the present invention was effective and completed the present invention. Thus, according to the invention, an adsorbent comprising a microporous oxide composite containing silica and titania in a weight ratio of 72:25 to 0:100 and having a specific surface area of at least 50 m ² /g is provided. The adsorbent of the present invention is a synthetic inorganic adsorbent composed of a composite of inorganic oxides mainly consisting of silica (SiO ₂ ) and titania (TiO ₂ ). Although its exact structure is not clear, for example, a fine matrix region consisting of silica and a fine matrix region consisting essentially of titania have the following formula: Connect three-dimensionally through the bond shown in
It is believed to form a microporous oxide complex mass. According to the present invention, the composite requires a weight ratio of silica to titania of at least 75:25 to exhibit excellent adsorption properties, and as the ratio of titania to silica increases, It was found that even when the titania content is substantially 100%, the adsorption capacity is increased. Therefore, in the adsorbent of the present invention, it should be understood that the expression "oxide complex" includes cases where the adsorbent is composed only of titania as an exception. Therefore, the oxide composite of the present invention contains silica and titania in a weight ratio of 75:25 to 0:100, preferably
It can be contained in a ratio of 50:50 to 10:90. Further, according to the present invention, the oxide complex further increases the adsorption ability for certain substances, such as dyes in dyeing waste liquid, by including metal oxides other than silica and titania as necessary. It was discovered that this can be achieved. As such metal oxides, basic metal oxides, such as alkaline earth metal oxides such as magnesium and calcium oxide; alumina, iron oxide, zirconia, etc. are preferable, and among them, magnesia, calcium oxide, alumina, and iron oxide are preferable. Used to advantage. The content of these metal oxides is not strictly limited, but if too large a quantity is used, it will have a negative effect on the inherent adsorption ability of the silica-titania composite, so generally the total weight of silica and titania is It is desirable to keep the content to 30% by weight or less, preferably 25% by weight or less, and more preferably 20% by weight or less. The oxide composite used in the adsorbent of the present invention has a microporous structure and a high specific surface area. That is, the adsorbents of the present invention generally have a specific surface area of at least 50 m ² /g, preferably greater than 120 m ² /g, and usually within the range of about 200 to about 350 m ² /g. In this specification, "specific surface area" is
S. Brunaur, PHEmmett and E. Teller, J.Am.
It refers to the specific surface area when measured by the BET method described in Chem.Soc., 60 , 309 (1938). The adsorbent of the present invention generally has many very fine pores with an average pore size of about 300 angstroms or less, usually about 200 angstroms or less, although it varies depending on the manufacturing conditions described below. The total pore volume is generally at least about 0.6 cm ³ /g as measured by mercury porosimetry.
, typically in the range of about 1.0 to 1.4 cm ³ /g, and for pore sizes less than 200 angstroms, the pore volume is generally at least 0.2 cm ³ /g, usually about 0.3 to 1.0
It is in the range of cm ³ /g. Further, the adsorbent of the present invention can have a bulk specific gravity, depending on its composition, generally in the range of 0.2 to 0.9 g/cm ³ , preferably 0.35 to 0.6 g/cm ³ . According to the present invention, a microporous oxide composite having the physical properties as described above is prepared by adding an acidic aqueous solution containing a soluble titanium salt and a soluble silicate, if necessary together with other soluble metal salts, to an alkaline hydration solution. Upon decomposition, the silica and titania are co-precipitated with other metal oxides, if present, and the resulting precipitate is isolated and dried, optionally containing approximately
It can be manufactured by firing at a temperature of 800°C or lower. Examples of soluble titanium salts that can be used as raw materials include titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium isopropoxide, etc.
Further, as the soluble silicate, for example, sodium meta- and orthosilicate, water glass, silicon tetrachloride, ethyl silicate, silica sol, etc. can be used.
Furthermore, other soluble metal salts that can be added as appropriate include magnesium chloride, magnesium carbonate, aluminum chloride, aluminum sulfate, aluminum nitrate, ferric chloride, iron sulfate, calcium chloride, and the like. The above-mentioned soluble titanium salt and soluble silicate can each be mixed in the form of an aqueous solution. The concentration of the titanium salt and silicate in each aqueous solution is not critical, but each generally ranges from 0.01 to 0.6.
Advantageously, the concentration is in the range 0.1 to 0.4 mol/mol/, preferably 0.1 to 0.4 mol/. The aqueous solution of the titanium salt is generally acidic, whereas the aqueous solution of the silicate is generally alkaline. Therefore, simply mixing the two aqueous solutions causes a neutralization reaction, and the titanium salt and the silicate are hydrolyzed to form silica. A mixed gel of titania and titania is produced, but the mixed gel thus produced does not provide an oxide complex with adsorption capacity sufficient to withstand use as an adsorbent. However, in the present invention, an aqueous solution of a soluble silicate is adjusted in advance to be acidic with a pH of about 0.1 to 4, and then mixed with an aqueous solution of a soluble titanium salt, and then the mixed aqueous solution is subjected to alkaline hydrolysis. It has been found that by adding the above, an oxide composite with extremely excellent performance can be obtained as shown in the Examples below. The mixing ratio of the aqueous solution of soluble silicate and aqueous solution of soluble titanium salt can be varied depending on the weight ratio of silica to titania required in the final composite. The alkaline hydrolysis is accomplished by adding an alkali to the resulting mixed aqueous solution. Usable alkalis include compounds that decompose and release ammonia by heating under hydrolysis conditions, such as urea and urotropin, or inorganic alkalis, such as ammonia water, caustic soda, caustic potash, and soda carbonate. Compounds that liberate ammonia, such as urea and urotropin, are preferred. It is desirable to proceed with the hydrolysis as slowly as possible to avoid rapid coprecipitation. Therefore, it is advantageous to slowly add the alkali to the mixed aqueous solution and raise the pH of the solution very slowly, thereby gradually co-precipitating the silica-titania. For this purpose, it is particularly advantageous to gradually add aqueous ammonia, which is a relatively weak alkali, or to use ammonia-releasing compounds such as urea or urotropin, which are added to the mixed aqueous solution. Even if ammonia is added all at once, the PH of the liquid does not rise rapidly, and ammonia can be gradually decomposed and liberated by heating, so rapid coprecipitation can be avoided. The above alkali is added to the mixed aqueous solution after hydrolysis.
It is appropriate to use the amount such that the pH falls within the range of about 6.0 to 8.0. The temperature during the hydrolysis varies depending on the type of alkali used, and when using aqueous ammonia or the above inorganic alkali, room temperature is sufficient, but if necessary, the temperature may be raised to about 60°C. You can warm it up. Additionally, when using compounds that release ammonia upon thermal decomposition, such as urea or urotropin, it is advantageous to heat to temperatures of about 80 to about 105°C; It is preferable to continue until most of the silicates and titanium salts are precipitated as silica and titania.
It can be completed in about 5 hours. The deposited precipitate can then be separated from the aqueous solution by conventional methods such as filtration, centrifugation, etc., and the separated precipitate is dried. The drying may be carried out by either air drying or heat drying. The composite thus obtained can be used as an adsorbent in the form of a powder, or can be used in the form of (granules),
It may be used as an adsorbent after being formed into any shape such as pellet, film, rod, ring, etc. Further, the composite is calcined at a temperature of up to about 800°C, preferably between about 400 and about 700°C.
The hardness of the composite can be increased, thereby improving its ease of handling as an adsorbent. The composite prepared as described above has the above-mentioned physical properties, has extremely excellent adsorption ability, and can be used for various purposes as described below. However, according to the present invention, it has been found that when the composite prepared as described above is treated with an aqueous alkaline solution, the adsorption capacity for metal ions and reactive dyes increases by about 10 to 60%. Examples of the alkali that can be used in such alkali treatment include alkali metal hydroxides, carbonates, or bicarbonates such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate; barium oxide,
Alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide: ammonia water and the like are preferred, and compounds of sodium, potassium and barium are particularly preferred. Such alkali has a concentration of about 0.1 to about 6N, especially about 0.5N.
After preparing an aqueous solution of ~2N, it is used to treat the composite obtained above. The treatment involves immersing the composite in the aqueous solution for at least 5 hours, preferably
This can be done by leaving it for about 12 to 24 hours. After separation from the alkaline aqueous solution, the thus treated composite is thoroughly washed with water, dried and, if necessary, heated to a temperature below about 800°C, especially about
Further calcination may be performed at a temperature of 400 to about 700°C. The reason why the adsorption capacity of the composite is improved by the above alkali treatment is unknown, but the reason is that the micropore surface of the microporous composite is activated by the alkali treatment, or the micropore surface is coated with alkali metal or alkali. It is thought that the earth metal remains in the form of an oxide, which has a very favorable effect on the adsorption of the composite. In fact, for example, a silica-titania (50/50 weight ratio) composite treated with an aqueous sodium hydroxide solution retains about 0.3% by weight of sodium oxide after firing at about 600°C, as measured by flame spectroscopy. It has been confirmed that In addition, such an alkali-treated composite has an increased specific surface area and a decreased average pore diameter compared to an untreated composite. For example, in the case of an untreated silica-titania composite (weight ratio 50/50), the specific surface area is about 220 to about 260 m ² /g, and the average pore diameter is about
100 to about 140 angstroms, but when treated with an aqueous sodium hydroxide solution, the specific surface area becomes about 250 to about 290 m ² /g and the average pore diameter becomes about 70 to about 90 angstroms.
The removal rate of chromium ions in an aqueous solution containing 10 ppm was significantly improved from 64% to 93% at pH 2. In addition, silica-titania composites treated with barium hydroxide tend to have significantly improved adsorption capacity for metal ions at high pH compared to untreated ones. The adsorbent of the present invention can contain various metal ions, such as chromium, as will be demonstrated in the examples below.
Efficiently remove metal ions and organic substances from industrial wastewater that contains various concentrations of organic substances such as dyes and organic solvents as well as ions of metals such as mercury, cadmium, lead, arsenic, zinc, and nickel. Can be easily separated or removed. The adsorbent of the present invention has a large adsorption capacity and a high adsorption rate for the metal ions and organic substances mentioned above, and can adsorb and remove these substances very effectively from a waste liquid containing such substances in a short period of time. Moreover, the adsorbent of the present invention not only has a large adsorption capacity and adsorption rate, but also has a very high removal rate of metal ions and organic substances even from liquids containing metal ions and organic substances at extremely dilute concentrations. It can then be removed. For example, the silica-titania of the present invention (weight ratio
50/50) composite adsorbent has a low equilibrium concentration of chromium ions of 0.1 ppm in aqueous solution.
It has an extremely high adsorption capacity of 0.21 mg chromium/g adsorbent. Furthermore, the adsorbent of the present invention can easily desorb the adsorbed substance. For example, by recovering the adsorbent that has adsorbed metal ions from the treatment solution and then immersing it in an aqueous solution with an appropriate pH. , the adsorbent material can be easily and almost completely desorbed from the adsorbent. Further, desorption of organic substances such as dyes can be carried out extremely easily by thermal evaporation or thermal decomposition of the adsorbed organic substances, taking advantage of the excellent heat resistance of the adsorbent of the present invention. It goes without saying that the adsorbent thus desorbed can be reused. Moreover, the adsorbent thus desorbed can be used again to adsorb metal ions and various organic substances, and the adsorbent of the present invention can be used for adsorption multiple times.
It has the great advantage of being able to be reused in desorption cycles without substantial loss of adsorption capacity. Furthermore, by using the adsorbent of the present invention, it is possible to recover and concentrate metal ions in an aqueous solution containing metal ions at a dilute concentration. That is, using the adsorbent of the present invention, metal ions are adsorbed and separated from an aqueous solution containing metal ions at a dilute concentration. The adsorbent of the present invention that has adsorbed the metal ions is immersed in an aqueous solution for desorption having an appropriate pH, and the metal ions are eluted into the aqueous solution. The adsorbent from which the metal ions have been desorbed is immersed in an aqueous solution containing the same metal ions as described above to perform an adsorption operation, and then returned to the aqueous solution from which the desorption was performed, and the adsorbed metal ions are eluted into the aqueous solution. urge By repeating this operation,
The concentration of metal ions in the desorption aqueous solution can be increased, and as a result, the dilute metal ion-containing aqueous solution is concentrated to an aqueous solution containing the metal ions at a higher concentration. As described above, the adsorbent of the present invention has a wide range of uses as an adsorbent for various organic substances including various metal ions and dyes. Next, the present invention will be explained in more detail with reference to Examples. Example 1 One each of a 0.2 mole sodium metasilicate solution acidified with hydrochloric acid (PH = approximately 1) and a titanium tetrachloride solution of the same concentration were placed in three flasks together with 2 moles of urea, and stirred with a magnetic stirrer. Meanwhile, a silica-titania co-precipitated gel was uniformly precipitated by heating at 90° C. for 5 to 6 hours in an oil bath. Then, it is filtered, thoroughly washed with water until ammonia is no longer detected, and then dried at 110°C overnight. The powder thus obtained was formed into a cylindrical shape of 10 mm x 25 mmφ, and then solidified in an electric furnace at 600°C for 1 hour.
The mixture was sieved to 20 to 42 meshes to obtain a granular adsorbent made of a silica-titania composite. The physical properties of this adsorbent were as shown in Table 1 below.

[Table] The adsorption performance of the adsorbent obtained above was investigated using the method described below. 25 ml of a solution prepared using potassium dichromate so that the concentration of chromium ions was 10 ppm and 150 mg of the adsorbent were placed in a 100 ml stoppered Erlenmeyer flask, shaken in a thermostatic bath for 24 hours, and then subjected to atomic absorption spectrometry (JIS). The concentration of chromium remaining in the solution was determined according to K0102, 51.1.2), and the removal rate was calculated using the following formula. Removal rate (%) = initial concentration (ppm) - residual concentration (ppm) / initial concentration (ppm) x 100 At this time, the initial pH of the chromium ion solution was adjusted using hydrochloric acid or sodium hydroxide solution.
The relationship between initial pH and removal rate is shown in Table 2 below.

[Table] Example 2 The granular adsorbent of the silica-titania composite obtained in Example 1 was shaken in a 1N sodium hydroxide solution for 12 hours, thoroughly washed with water, and dried at 110°C overnight to remove the alkali content of the adsorbent. I processed it. The physical properties of the adsorbent at this time are shown in Table 3 below. Also,
An adsorption test similar to that in Example 1 was conducted using this adsorbent. At this time, in addition to chromium, similar adsorption tests were conducted on solutions containing cadmium, zinc, lead, and nickel, all prepared to a concentration of 1 ppm using nitrates or chlorides, and the results are shown in Table 4 below. show.

【table】

[Table] Example 3 In Example 1, by changing the amounts of sodium metasilicate solution and titanium tetrachloride solution,
A co-precipitated gel with a weight ratio of SiO ₂ /TiO ₂ ranging from 90/10 to 0/100 was precipitated, and an adsorption test similar to that in Example 1 was conducted as a particulate adsorbent at pH 2. In addition, the adsorbent was treated with alkali and the results are shown in Table 5 below.

[Table] Example 4 In Example 1, urea was used as a precipitant for the mixed solution of sodium metasilicate and titanium tetrachloride,
Instead of uniformly precipitating the coprecipitated gel, 6N ammonia water was placed in a beaker and gradually dropped into the mixed solution until the pH reached 8, and the coprecipitated gel was precipitated heterogeneously. The same adsorption test was carried out after alkaline treatment of the adsorbent. The results are shown in Table 6 below.

[Table] Example 5 The alkaline treatment of the adsorbent in Example 2 was
Instead of 1N sodium hydroxide solution, use 1N potassium hydroxide solution, saturated barium hydroxide solution or 1N
Aqueous ammonia was used in each case, and the adsorption tests obtained were then carried out in the same manner as in Example 1. The results are shown in Table 7 below.

[Table] Example 6 Prepared as in Example 1 except that half the volume of the same titanium tetrachloride solution used in Example 1 was replaced with an aqueous solution of magnesium chloride, calcium chloride, or aluminum chloride at a concentration of 0.2 mole/. A three-component co-precipitated gel was obtained from the same mixed solution as in Example 1, and an adsorbent was further manufactured using this gel. An adsorption test similar to that in Example 1 was conducted, and the results are shown in Table 8 below.

[Table] Example 7 The adsorbent prepared in Example 6 was treated with alkali in the same manner as in Example 2, and the resulting alkali-treated adsorbent was subjected to an adsorption test. The results are shown in Table 9 below.

[Table] Example 8 Using the adsorbent prepared in Example 2 (treated with alkali), the relationship between the removal rate and adsorption time of chromium ions, cadmium ions, and zinc ions is as follows:
The optimum pH for adsorption in each solution was determined. Regarding chromium, a similar relationship was determined using the adsorbent treated with alkali (ammonia water treatment) prepared in Example 3. The results are shown in Table 10 below.

【table】

[Table] Example 9 150 mg of the adsorbent prepared in Example 2 was added to 25 ml of each solution containing various initial concentrations of chromium ions, cadmium ions, or zinc ions and shaken, and the saturation adsorption when adsorption equilibrium was reached. The relationship between the amount and the equilibrium concentration is shown in Table 11 below, and all of these satisfied the Freundlich type adsorption isotherm.

[Table] Example 10 The adsorbent prepared in Example 2 was shaken in a solution with an initial concentration of chromium ions of 10 ppm and an initial pH of 2 for 24 hours to fully reach adsorption equilibrium, and then the adsorbent was separated. Approximately 90% of the adsorbed chromium was eluted by shaking in 1N sodium hydroxide solution. At the same time, the adsorption capacity of the adsorbent was completely recovered. This adsorption and elution operation was repeated six times, but as shown in Table 12 below, no decrease in either adsorption or elution ability was observed.

[Table] Example 11 1.0 g of the adsorbent prepared in Example 2 was added to 500 ml of a solution containing 10 ppm of chromium ions (hereinafter referred to as "stock solution"), and the same adsorption test as described in Example 1 was conducted. However, 91% of chromium was adsorbed. Then, the same elution procedure as described in Example 10 was performed in 10 ml of 1N sodium hydroxide solution, and as a result, almost 100% of the adsorbed chromium was eluted, and the chromium concentration in this solution was 455 ppm, resulting in the above The chromium ion concentration of the stock solution increased from 10ppm to 455ppm.
A strong two-fold concentration was achieved. Example 12 Using the adsorbent prepared in Example 2, 10ppm
of chromium ions, 1ppm of cadmium ions and
As a result of investigating the selective adsorption performance from a mixed solution containing the three 1ppm zinc ions using the same adsorption test method described in Example 1, mixed or selective adsorption properties as shown in Table 13 below were achieved. It was done.

[Table] Example 13 Using the adsorbents prepared in Examples 1 and 6, acid dye (CIAcid Blue 40) and basic dye (C.
The adsorption performance of I.Basic Blue 3) was investigated by the method below, and the results are shown in Tables 14 and 15 below. 50ml of an aqueous solution (raw water) in which the dye was dissolved to a concentration of 100ppm and 200mg of the above adsorbent were added.
A 100 ml stoppered Erlenmeyer flask is shaken in a constant temperature bath maintained at 20°C, and after a predetermined period of time, 5 ml of the solution is collected and filtered through a 0.45μ membrane filter. The absorption spectrum of the obtained liquid was measured, and the decolorization rate was calculated from the area ratio with the absorption spectrum of the raw water.

【table】

[Table] Example 14 50 ml each of aqueous solutions containing CIAcid Blue 40 or CIBasic Blue 3 at concentrations of 60, 80, 100, 150, and 200 ppm were prepared, and the former (CIAcid Blue
Silica-titania-magnesia was added to the dye solution of 40), and 100 mg of silica-titania was added to the dye solution of the latter (CIBasic Blue 3), and the mixture was shaken in a constant temperature bath at 20°C to reach adsorption equilibrium. rear,
The decolorization rate was determined in the same manner as above, and the results are shown in Section 16 below.
Shown in the table. The saturated adsorption amount and equilibrium concentration at this time are
It followed a Freundlich-type adsorption isotherm.

【table】

[Table] Example 15 Using the adsorbents prepared in Examples 1 and 2, an adsorbent similar to that described in Example 13 was prepared for reactive dye (CIReactive Red 2), which is said to be the most difficult to treat wastewater. After conducting the test, the following
The results shown in Table 17 were obtained.

[Table] Example 16 The adsorbent prepared in Example 1 was treated in the same manner as above.
After adsorbing CIBasic Blue 3, 1 at 600℃
After heating for a period of time, the adsorbent returned to its initial white color and its adsorption capacity was completely restored. This adsorption and thermal decomposition operation was repeated 5 times for the same adsorbent.
No decrease in adsorption capacity was observed at all. In addition, the silica-titania prepared in Example 6
CIAcid Blue 40 was adsorbed onto the magnesia complex and the same desorption operation as above was repeated, but again no decrease in adsorption capacity was observed. Example 17 Using the adsorbent prepared in Example 1, adsorption and removal of total organic carbon (TOC) from wastewater from a certain dyeing factory was investigated. 100ml of wastewater 50ml with 200mg of the adsorbent added
After shaking the stoppered Erlenmeyer flask in a constant temperature bath at 20℃ for a specified period of time, TOC was measured and compared with wastewater.
The TOC removal rate was determined and the results are shown in Table 18 below. At this time, hydrochloric acid was added to the wastewater in advance to adjust the pH.

【table】

Claims (1)

[Claims] 1 Silica and titania in a weight ratio of 75:25 to 0:
A coprecipitated gel or a fired product thereof containing a metal oxide selected from magnesia, calcium oxide, alumina, and iron oxide in an amount of 30% by weight or less based on the total weight of silica and titania. and having a specific surface area of at least 50 m ² /g. 2. The adsorbent according to claim 1, wherein the oxide composite contains silica and titania in a weight ratio of 50:50 to 10:90. 3. The adsorbent of claim 1, wherein the oxide complex has a specific surface area of at least 120 m ² /g. 4. Subjecting an acidic aqueous solution containing dissolved soluble titanium salt, or soluble titanium salt and soluble silicate, or soluble titanium salt, soluble silicate, and soluble salt of a metal selected from magnesium, calcium, aluminum, and iron to alkaline hydrolysis. silica and titania or silica, titania and oxides of the metals mentioned above are co-precipitated; the resulting precipitate is separated, dried and, if necessary, calcined at a temperature below about 800°C. A method for producing an adsorbent made of an oxide complex with increased adsorption capacity, characterized in that the obtained oxide complex is then treated with an aqueous alkaline solution. 5. The method according to claim 4, wherein the acidic aqueous solution has a pH of 0.1 to 4. 6. The method according to claim 4, wherein the alkaline aqueous solution has a normality of 0.1 to 6.