Patent Application
20130092625
The present invention relates to a composite magnesium hydroxide containing a carbonate ion and having a large BET specific surface area, a method for producing the same and an adsorbent comprising the same.
Magnesium hydroxide has been known for a long time and is widely used to adsorb (neutralize) an acid substance as it is a solid base. For example, it is used as an antacid in the medical field, as a flue-gas desulfurizing agent or a drainage neutralizer in the industrial field and as an acid soil neutralizer in the agricultural field. For the adsorption (neutralization) of an acid substance, it is desired that magnesium hydroxide should have a large contact area with an acid substance, that is, a large BET specific surface area. As the method for producing magnesium hydroxide, there are known a seawater method in which seawater is reacted with slaked lime and a hydration method in which magnesium oxide is hydrated with decarbonated water. However, the BET specific surface areas of magnesium hydroxide particles synthesized by these methods are not larger than 80 m2/g
As the method for obtaining a magnesium hydroxide particle having a large BET specific surface area, there is known a method in which a divalent anion for inhibiting the crystal growth of magnesium hydroxide is added in the step of producing magnesium hydroxide. That is, when a magnesium salt solution and an alkali metal hydroxide or ammonia water are reacted with each other in the presence of a carbonate ion, a carbonate group-containing magnesium hydroxide containing a carbonate group and having a BET specific surface area of 80 m2/g or more is obtained (Patent Document 1). This carbonate group-containing magnesium hydroxide is an extremely effective acid gas adsorbent as it reacts with hydrogen chloride gas, SOx gas and acetic acid-based gas instantaneously. However, it is not so effective for hydrogen sulfide gas and methyl mercaptan.
It is therefore an object of the present invention to provide a composite magnesium hydroxide having excellent adsorption performance for not only hydrogen chloride gas, SOx gas and acetic acid-based gas but also hydrogen sulfide gas and methyl mercaptan and a large BET specific surface area as well as a method for producing the same. It is another object of the present invention to provide an adsorbent comprising this composite magnesium hydroxide.
The inventors of the present invention conducted intensive studies to improve the above problem and found that a composite magnesium hydroxide having excellent adsorption performance for hydrogen sulfide and methyl mercaptan is obtained by supporting a metal hydroxide such as Cu or Zn on the surface of a magnesium hydroxide particle containing a carbonate group and having a large BET specific surface area. The present invention was accomplished based on this finding.
The composite magnesium hydroxide of the present invention is represented by the following formula (1).
Mg1-xMx(OH)2-y(CO3)0.5y.mH2O (1)
In the above formula, M is at least one divalent metal ion selected from the group consisting of Zn2+, Cu2+, Ni2+, Co2+, Ca2+, Mn2+, Fe2+ and Ba2+.
The metal ion can be selected according to a substance to be adsorbed. For example, when hydrogen sulfide gas is to be adsorbed, it is preferred to compound Cu2+, Ni2+ or Zn2+. Especially Cu2+ and Ni2+ have a high hydrogen sulfide gas adsorption speed and excellent stability.
In the above formula, x satisfies 0<x≦0.5, preferably 0<x≦0.2, more preferably 0<x≦0.1.
In the above formula, y satisfies 0.02≦y≦0.7, preferably 0.04≦y≦0.6, more preferably 0.1≦y≦0.4.
In the above formula, m satisfies 0≦m≦1, preferably 0≦m≦0.6, more preferably 0≦m≦0.4.
The composite magnesium hydroxide of the present invention has a BET specific surface area of 100 to 400 m2/g, preferably 120 to 350 m2/g, more preferably 150 to 300 m2/g.
The present invention includes a baked product obtained by baking the above composite magnesium hydroxide at 350° C. or higher.
The composite magnesium hydroxide of the present invention can be manufactured by adding and mixing an aqueous solution of a salt of at least one divalent metal selected from the group consisting of Zn2+, Cu2+, Ni2+, Co2+, Ca2+, Mn2+, Fe2+ and Ba2+ with a slurry of a carbonate group-containing magnesium hydroxide having a BET specific surface area of 100 m2/g or more to support a divalent metal hydroxide on the surface of the carbonate group-containing magnesium hydroxide.
The composite magnesium hydroxide of the present invention is obtained from a slurry of a carbonate group-containing magnesium hydroxide having a BET specific surface area of 100 m2/g or more (may be referred to as “raw material slurry” hereinafter).
The raw material slurry can be manufactured by reacting a water-soluble magnesium salt with an alkali metal hydroxide or ammonia water in water in the presence of a carbonate.
Examples of the water-soluble magnesium salt include magnesium sulfate, magnesium chloride, magnesium nitrate and magnesium acetate.
Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Ammonia water may be used in place of the alkali metal hydroxide.
Examples of the carbonate include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and ammonium carbonate.
The reaction temperature is preferably 5 to 60° C. The reaction time is preferably 3 to 180 minutes. Washing is preferably carried out bypassing water which is 5 to 50 times the weight of the solid content or by emulsification. The drying temperature is preferably 90 to 350° C.
The crystal growth of magnesium hydroxide is inhibited by reacting the water-soluble magnesium salt with the alkali metal hydroxide or ammonia water in the presence of the carbonate, thereby making it possible to obtain the carbonate group-containing magnesium hydroxide having a large BET specific surface area.
The divalent metal is at least one selected from the group consisting of Zn2+, Cu2+, Ni2+, Co2+, Ca2+, Mn2+, Fe2+ and Ba2+. Salts thereof include chlorides, sulfates, nitrates and acetates. Specific examples thereof include zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, copper chloride, copper sulfate, copper nitrate, copper acetate and nickel chloride.
The divalent metal can be supported by adding and mixing an aqueous solution of the divalent metal salt to a slurry of the carbonate group-containing magnesium hydroxide.
The supporting temperature is preferably 5 to 60° C. The supporting time is preferably 5 to 120 minutes.
Thus, when the carbonate group-containing magnesium hydroxide having a large BET specific surface area is prepared and an aqueous solution of a salt of a divalent metal such as Zn or Cu is added to a slurry of the carbonate group-containing magnesium hydroxide, many types of composite magnesium hydroxides can be easily synthesized according to purpose and the divalent metal ion to be compounded is eccentrically located on the surface of each particle, thereby making it easy to obtain the effect of the divalent metal ion with a small amount thereof.
The composite magnesium hydroxide of the present invention can be manufactured by contacting an Mg ion, at least one divalent metal ion selected from the group consisting of Zn2+, Cu2+, Ni2+, Co2+, Ca2+, Mn2+, Fe2+ and Ba2+, and an OH ion to one another in water in the presence of a CO3 ion.
The composite magnesium hydroxide of the present invention can also be synthesized by reacting a mixed metal salt aqueous solution containing a magnesium salt and another metal salt such as a Zn or Cu salt with an alkali substance in the presence of a CO3 ion. However, when magnesium hydroxide is used as an adsorbent, the composite magnesium hydroxide is preferably synthesized by precipitating a metal hydroxide such as Cu or Zn hydroxide on the surface of a magnesium hydroxide particle because the effect of Cu or Zn can be obtained with a small amount of the metal advantageously. However, since an aqueous solution of Cu or Zn has mild acidity, when the production method (1) is employed, the BET specific surface area decreases slightly as compared with that before support. The production method (2) does not have this problem.
The reaction method is the same as the method for producing the raw material slurry described in the production method (1) except that an aqueous solution of a water-soluble magnesium salt is changed to an aqueous solution obtained by mixing together a water-soluble magnesium salt and an aqueous solution of a water-soluble salt of divalent metal such as a Zn or Cu.
The present invention includes an adsorbent comprising the above composite magnesium hydroxide. The adsorbent preferably comprises a granulated product obtained by granulating the composite magnesium hydroxide to a particle diameter of 0.05 to 20 mm. When the adsorbent is filled into a column and an acid gas is circulated into the column, a spray granulated product or an extrusion granulated product is excellent in terms of air permeability and gas contact ability.
The adsorbent is preferably used to adsorb an acid gas. The adsorbent is preferably used to adsorb an acid substance contained in an organic solvent. The adsorbent is preferably used for deodorization.
The present invention includes a chemical filter containing the above composite magnesium hydroxide.
To adsorb a hydrogen sulfide gas or methyl mercaptan, X in the formula (1) of the composite magnesium hydroxide is preferably 0.001 or more, more preferably 0.01 or more.
The following examples are provided to further illustrate the present invention.
12 liters of a 1.5 mol/L magnesium sulfate aqueous solution and 11.4 liters of an alkali mixed solution of caustic soda and sodium carbonate having a total alkali concentration of 3.0 N (2NaOH:Na2CO3=90:10) were subjected to a continuous pouring addition reaction at room temperature under agitation for a residence time of 10 minutes. About 23.4 liters of the obtained reaction slurry was filtered, washed by passing through 21 liters of water, dehydrated and dried at 105° C. with a shelf-type drier for 18 hours. The dried product was ground in a mortar and let pass through a metal net having an opening of 150 μm to obtain 1,040 g of a white powder having a BET specific surface area of 260 m2/g and represented by the following formula.
Mg(OH)1.80(CO3)0.10.0.10H2O
500 ml of water was added to 50 g of this white powder, and 43.2 ml of a 1.0 mol/L zinc chloride aqueous solution was added to the resulting suspension under agitation and kept stirred at room temperature for 30 minutes. The obtained reaction slurry was filtered, washed by passing through 1 liter of water, dehydrated and dried at 105° C. with a shelf-type drier for 18 hours. The dried product was ground in a mortar and let pass through a metal net having an opening of 150 μm to obtain 48.9 g of a white powder having a BET specific surface area of 206 m2/g and represented by the following formula.
Mg0.95Zn0.05(OH)1.76(CO3)0.12.0.11H2O
12 liters of a 1.5 mol/L magnesium sulfate aqueous solution and 11.4 liters of an alkali mixed solution of caustic soda and sodium carbonate having a total alkali concentration of 3.0 N (2NaOH:Na2CO3=90:10) were subjected to a continuous pouring addition reaction at room temperature under agitation for a residence time of 10 minutes. About 23.4 liters of the obtained reaction slurry was filtered, washed by passing through 21 liters of water, dehydrated and dried at 105° C. with a shelf-type drier for 18 hours. The dried product was ground in a mortar and let pass through a metal net having an opening of 150 μm to obtain 1,040 g of a white powder having a BET specific surface area of 260 m2/g and represented by the following formula.
Mg(OH)1.80(CO3)0.10.0.10H2O
500 ml of water was added to 50 g of this white powder, and 43.2 ml of a 1.0 mol/L copper sulfate aqueous solution was added to the resulting suspension under agitation and kept stirred at room temperature for 30 minutes. The obtained reaction slurry was filtered, washed by passing through 1 liter of water, dehydrated and dried at 105° C. with a shelf-type drier for 18 hours. The dried product was ground in a mortar and let pass through a metal net having an opening of 150 μm to obtain 49.3 g of an aqua powder having a BET specific surface area of 214 m2/g and represented by the following formula.
Mg0.95Cu0.05(OH)1.80(CO3)0.10.0.14H2O
12 liters of a 1.5 mol/L magnesium sulfate aqueous solution and 11.4 liters of an alkali mixed solution of caustic soda and sodium carbonate having a total alkali concentration of 3.0 N(2NaOH:Na2CO3=90:10) were subjected to a continuous pouring addition reaction at room temperature under agitation for a residence time of 10 minutes. About 23.4 liters of the obtained reaction slurry was filtered, washed by passing through 21 liters of water, dehydrated and dried at 105° C. with a shelf-type drier for 18 hours. The dried product was ground in a mortar and let pass through a metal net having an opening of 150 μm to obtain 1,040 g of a white powder having a BET specific surface area of 260 m2/g and represented by the following formula.
Mg(OH)1.80(CO3)0.10.0.10H2O
500 ml of water was added to 50 g of this white powder, and 43.2 ml of a 1.0 mol/L nickel chloride aqueous solution was added to the resulting suspension under agitation and kept stirred at room temperature for 30 minutes. The obtained reaction slurry was filtered, washed by passing through 1 liter of water, dehydrated and dried at 105° C. with a shelf-type drier for 18 hours. The dried product was ground in a mortar and let pass through a metal net having an opening of 150 μm to obtain 48.5 g of a pale-green powder having a BET specific surface area of 225 m2/g and represented by the following formula.
Mg0.94Ni0.06(OH)1.80(CO3)0.10.0.16H2O
12 liters of a 1.5 mol/L magnesium sulfate aqueous solution and 11.4 liters of an alkali mixed solution of caustic soda and sodium carbonate having a total alkali concentration of 3.0 N (2NaOH:Na2CO3=90:10) were subjected to a continuous pouring addition reaction at room temperature under agitation for a residence time of 10 minutes. About 23.4 liters of the obtained reaction slurry was filtered, washed by passing through 21 liters of water and emulsified with water to obtain 10 liters of an emulsion. This was dried with a spray drier to obtain 950 g of a white spray granulated powder having a BET specific surface area of 263 m2/g and represented by the following formula.
Mg(OH)1.80(CO3)0.10.0.18H2O
500 ml of water was added to 50 g of this white spray granulated powder, and 43.2 ml of a 1.0 mol/L zinc chloride aqueous solution was added to the resulting suspension under agitation and kept stirred at room temperature for 30 minutes. The obtained reaction slurry was filtered, washed by passing through 1 liter of water, dehydrated and dried at 105° C. with a shelf-type drier for 18 hours. The dried product was let pass through a metal net having an opening of 500 μm to obtain 48.0 g of a white powder having a BET specific surface area of 180 m2/g and represented by the following formula.
Mg0.94Zn0.06(OH)1.78(CO3)0.11.0.12H2O
12 liters of a 1.5 mol/L magnesium sulfate aqueous solution and 11.4 liters of an alkali mixed solution of caustic soda and sodium carbonate having a total alkali concentration of 3.0 N (2NaOH:Na2CO3=90:10) were subjected to a continuous pouring addition reaction at room temperature under agitation for a residence time of 10 minutes. About 23.4 liters of the obtained reaction slurry was filtered, washed by passing through 21 liters of water and emulsified with water to obtain 10 liters of an emulsion. This was dried with a spray drier to obtain 950 g of a white spray granulated powder having a BET specific surface area of 263 m2/g and represented by the following formula.
Mg(OH)1.80(CO3)0.10.0.18H2O
500 ml of water was added to 50 g of this white spray granulated powder, and 43.2 ml of a 1.0 mol/L copper sulfate aqueous solution was added to the resulting suspension under agitation and kept stirred at room temperature for 30 minutes. The obtained reaction slurry was filtered, washed by passing through 1 liter of water, dehydrated and dried at 105° C. with a shelf-type drier for 18 hours. The dried product was let pass through a metal net having an opening of 500 μm to obtain 48.5 g of an aqua powder having a BET specific surface area of 209 m2/g and represented by the following formula.
Mg0.94Cu0.06(OH)1.82(CO3)0.09.0.12H2O
Calcium hydroxide which is a special grade reagent was used. The BET specific surface area thereof was 13.2 m2/g.
The KISUMA 5 magnesium hydroxide of Kyowa Chemical Industry Co., Ltd. was used. The BET specific surface area thereof was 5.9 m2/g.
The Kyowa Suimag F magnesium hydroxide of Kyowa Chemical Industry Co., Ltd. was used. The BET specific surface area thereof was 57.6 m2/g.
12 liters of a 1.5 mol/L magnesium sulfate aqueous solution and 11.4 liters of an alkali mixed solution of caustic soda and sodium carbonate having a total alkali concentration of 3.0 N (2NaOH:Na2CO3=90:10) were subjected to a continuous pouring addition reaction at room temperature under agitation for a residence time of 10 minutes. About 23.4 liters of the obtained reaction slurry was filtered, washed by passing through 21 liters of water, dehydrated and dried at 105° C. with a shelf-type drier for 18 hours. The dried product was ground in a mortar and let pass through a metal net having an opening of 150 μm to obtain 1,040 g of a white powder having a BET specific surface area of 260 m2/g and represented by the following formula.
Mg(OH)1.80(CO3)0.10.0.10H2O
12 liters of a 1.5 mol/L magnesium sulfate aqueous solution and 11.4 liters of an alkali mixed solution of caustic soda and sodium carbonate having a total alkali concentration of 3.0 N (2NaOH:Na2CO3=90:10) were subjected to a continuous pouring addition reaction at room temperature under agitation for a residence time of 10 minutes. About 23.4 liters of the obtained reaction slurry was filtered, washed by passing through 21 liters of water and emulsified with water to obtain 10 liters of an emulsion. This was dried with a spray drier to obtain 950 g of a white spray granulated powder having a BET specific surface area of 263 m2/g and represented by the following formula.
Mg(OH)1.80(CO3)0.10.0.18H2O
The above Examples 1 to 5 and the above Comparative Examples 1 to 5 were analyzed by the following methods.
The measurement results of composition analysis and BET specific surface area are shown in Table 1.
Acid gas adsorption tests were conducted on the above Examples 1 to 5 and the above Comparative Examples 1 to 5 by the following methods. The results of the acid gas adsorption tests are shown in Tables 2 to 4.
0.5 g of a powder sample was filled into a glass column having an inner diameter of 14 mm together with glass wool. 94.1 ppm of a hydrogen chloride gas was flown into this column at a rate of 0.44 L/min to measure the concentration at the exit of the column with a detection tube. The breakthrough time was a time when the concentration at the exit of the column exceeded a supply concentration of 0.5% (0.5 ppm).
0.5 g of a powder sample was filled into a glass column having an inner diameter of 14 mm together with glass wool. 136 ppm of an SO2 gas was flown into this column at a rate of 0.44 L/min to measure the concentration at the exit of the column with a detection tube. The breakthrough time was a time when the concentration at the exit of the column exceeded a supply concentration of 0.5% (0.7 ppm).
30 mg of a powder sample was put into a 1-liter tedler bag, air was removed from the bag, and 99.1 ppm of a hydrogen sulfide standard gas was filled into the bag to measure the concentration of the hydrogen sulfide gas in the tedler bag along with time by using the GC-14B gas chromatography of Shimadzu Corporation (equipped with an FPD detector). The β,β′-oxydipropionitrile 25% was used as the packing column. As for a sample having a hydrogen sulfide removal rate of 100% within 180 minutes of adsorption, the gas in the tedler bag was removed, and 99.1 ppm of a hydrogen sulfide standard gas was filled into the bag to carry out the measurement again.
Hydrogen sulfide removal rate (%)=(gas concentration before adsorption−gas concentration after adsorption)/gas concentration before adsorption×100
The composite magnesium hydroxides having a large BET specific surface area of Examples 1 to 5 had a higher adsorption rate for all the acid gases used in the tests than those of the ordinary calcium hydroxide and magnesium hydroxide of Comparative Examples 1 to 3. Although the carbonate group-containing magnesium hydroxides having a large BET specific surface area of Comparative Examples 4 and 5 had high adsorptivity for hydrogen chloride gas and SOx gas, they had much lower adsorptivity for hydrogen sulfide gas than those of Examples 1 to 5 in which Zn, Cu or Ni was compounded.
The composite magnesium hydroxide of the present invention has an extremely large BET specific surface area. The composite magnesium hydroxide of the present invention has excellent adsorptivity for not only hydrogen chloride gas, SOx gas and acetic acid-based gas but also hydrogen sulfide gas and methyl mercaptan. Since a divalent metal such as zinc or copper is eccentrically located on the surface of magnesium hydroxide in the composite magnesium hydroxide of the present invention, the effect of compounding can be obtained by supporting a small amount of the divalent metal.
According to the production method of the present invention, a carbonate group-containing magnesium hydroxide having a large BET specific surface area is first synthesized and then an aqueous solution of a salt of a metal to be compounded is added to the carbonate group-containing magnesium hydroxide, thereby making it possible to easily obtain a composite magnesium hydroxide having a large BET specific surface area.
The composite magnesium hydroxide of the present invention may be also synthesized by reacting a mixed metal salt aqueous solution containing a magnesium salt and another metal salt such as a Zn or Cu salt with an alkali substance in the presence of a CO3 ion. With this method, a composite magnesium hydroxide containing a divalent metal such as zinc or copper uniformly dispersed therein and having a large BET specific surface area can be obtained and the reduction of the BET specific surface area by compounding can be prevented. When the production method is changed according to purpose, the distribution of the compounded metal can be selected.
The adsorbent of the present invention has excellent adsorptivity for not only hydrogen chloride gas, SOx gas and acetic acid-based gas but also hydrogen sulfide gas and methyl mercaptan.
Since the composite magnesium hydroxide of the present invention has a high reaction rate with an acid substance, it is useful as an acid substance adsorbent neutralizer having an immediate effect. It can be expected to be used in a wide variety of fields such as fillers, ceramic raw materials, food additives and antacids.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010-136148 | Jun 2010 | JP | national |
| 2010-247245 | Nov 2010 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP11/62874 | 5/31/2011 | WO | 00 | 12/12/2012 |
