JP4810512B2 - Method for producing a coagulant for iron-silica water treatment - Google Patents

Description

  The present invention relates to a novel method for producing a flocculant for water treatment comprising an iron-silica composite liquid. More specifically, the present invention relates to a method for producing a water treatment flocculant composed of an iron-silica composite liquid which hardly causes gelation during production and has improved storage stability.

  A water treatment method in which a flocculant is injected into the water or wastewater to agglomerate and precipitate to remove the suspended solids and other impurities from various water and wastewater. As the flocculant for this purpose, aluminum sulfate, polyaluminum chloride, ferric chloride and the like are used.

  Among the above flocculants, aluminum sulfate or polyaluminum chloride is widely used. When these flocculants are used, the amount of flocculant added must be increased when the water temperature decreases or the amount of organic matter in the water, such as algae, increases. However, since aluminum is an amphoteric metal, it becomes soluble aluminum, There is a problem that it remains in the treated water. In addition, the aluminum-based flocculant has a drawback in that the amount of the aluminum-based flocculant increases because the aggregating property decreases at a low water temperature.

  In order to solve the above problems, an iron-silica water treatment flocculant in which an iron salt is added to polymerized silicic acid (silica sol) has recently been proposed and partially put into practical use. Iron-silica water treatment flocculants are attracting attention because of their high agglomeration performance and the ability to reduce the agglomerates generated to the soil.

  Several production methods for efficiently producing an iron-silica water treatment flocculant have been proposed. For example, a silica sol is obtained by colliding a silicate aqueous solution with a mineral acid such as sulfuric acid at a speed of 5 m / s or more, and after aging the silica sol, an aqueous iron salt solution is added (see, for example, Patent Document 1) ). In addition, a method of adding a silicate aqueous solution to a mixed aqueous solution of ferric chloride and mineral acid (for example, see Patent Document 2) has been proposed.

  When a silica sol is produced by reacting a silicate aqueous solution with a mineral acid, gelation does not occur during the reaction, and in order to obtain a uniform sol, the amount of mineral acid is excessive and the pH of the resulting silica sol is lowered. There is a need. Usually, a water-soluble iron salt is acidic (for example, when alkali is added to an aqueous solution of a ferric salt, precipitation occurs). Accordingly, when an aqueous solution of an iron salt such as ferric chloride is added to the silica sol, the pH is further lowered. For this reason, in an iron-silica water treatment flocculant produced using a silicate aqueous solution, a mineral acid, and an iron salt as raw materials and adjusting the conditions so as not to cause gelation, the pH of the iron salt increases as the amount of iron salt increases. It must be lowered.

  In the iron-silica water treatment flocculant, it is known that pH has an important influence on stability and the like. For this reason, the ferric salt aqueous solution and the silicate aqueous solution have an iron concentration of 1 to 8%, A technique for producing a flocculant by direct reaction so that the silica concentration is in the range of 2 to 6% and the pH is in the range of 0.5 to 1.5 or more has been proposed (for example, see Patent Document 2). In this technique, in order to make the final pH within the above range, the acidity is adjusted in advance by adding a mineral acid to the aqueous ferric chloride solution. However, as a result of further trials by the present inventors, it was found that high stability cannot always be obtained when the iron concentration is high and the iron concentration relative to silica is high. Furthermore, when mixing the ferric salt aqueous solution and the silicate aqueous solution so as to achieve the above pH, there is a problem that silica precipitates easily occur due to partial gelation particularly in a region where the ratio of the silicate aqueous solution is large. There is also.

  On the other hand, when water treatment is performed with an iron-silica water treatment flocculant, the rate of iron injection into the water to be treated is important for its treatment capacity. That is, the amount of pollutant in water that can be treated by the flocculant is highly dependent on the amount of iron injected.

  The iron-silica water treatment flocculant can be produced by freely changing the ratio of iron and silica, but if a flocculant with a large ratio of silica to iron is used, it is inevitably treated when the same iron injection rate is used. The amount of silica used in the process increases, resulting in an increase in the amount of sludge generated after treatment. At present, sludge produced by water treatment often has to be discarded as industrial waste, so there is a small amount of silica (high percentage of iron) in order to reduce the amount of flocculant for iron-silica water treatment. Liked.

  However, there is a problem that the stability is deteriorated when the silica ratio of the iron-silica water treatment flocculant decreases (the ratio of iron increases). When the iron-silica water treatment flocculant with a silica concentration of 2% by mass was actually compared at 30 ° C., the iron-silica water treatment flocculant was stable for 2-3 months when the silicon / iron (molar ratio) was 3. However, when the silicon / iron molar ratio is 0.25, gelation occurs in about one week.

JP 2003-38908 A JP-A-11-90111 JP 2005-34746 A JP 2001-70708 A

  Accordingly, the present invention provides an iron-silica water treatment flocculant having a small silicon / iron molar ratio and a high iron concentration in order to reduce the amount of sludge generated, without causing silica precipitation. It is an object of the present invention to provide a method for producing and improving stability during storage.

  In light of the above problems, the present inventors have continued intensive studies. As a result, firstly, the higher the iron concentration, the lower the pH needs to be stably produced without producing silica precipitates from the iron-silica composite liquid, and the iron-silica. It has also been found that the pH range in which the storage stability of the composite liquid can be improved also decreases as the iron concentration increases, and that both pH ranges are different in a region where the molar ratio of silicon / iron is small. As a result of further investigation based on these findings, the present invention has been completed.

That is, the present invention relates to an aqueous solution containing an iron salt, an aqueous silicate solution, and an inorganic acid, wherein the ratio of silicon to iron is 0.1 ≦ (silicon / iron) <1, the pH is less than 1, the iron concentration and the pH. Is the following formula (1),
−0.14 × iron concentration (mass%) + 1.4> pH (1)
Then, an iron-silica composite solution is prepared by mixing so as to satisfy the above relationship, and then an alkali is added to the composite solution, and the relationship between iron concentration and pH is expressed by the following formula (2).
−0.14 × iron concentration (mass%) + 1.4 <pH <−0.06 × iron concentration (mass%) + 1.2 (2)
PH is adjusted so as to satisfy the following conditions: water treatment aggregation comprising an iron-silica composite liquid in which the ratio of silicon and iron is in the range of 0.1 ≦ (silicon / iron) <1 in molar ratio It is a manufacturing method of an agent.

  According to the present invention, since the iron-silica composite liquid is produced so as to have a low pH at which silica precipitates are not easily generated by partial gelation, productivity is improved. Moreover, since this pH should just be below a fixed value, exact management, such as a raw material ratio, becomes unnecessary. And the stability at the time of a preservation | save can be improved greatly by the very simple method of adding an alkali with respect to the iron-silica composite liquid obtained in this way. This makes it difficult for gelation to occur when transporting an iron-silica water treatment flocculant having a large water treatment capacity (high iron concentration), so that the transportation cost and the like can be reduced. The utility value is extremely high.

In the production method of the present invention, first, an aqueous solution containing an iron salt, an aqueous silicate solution, and an inorganic acid, the molar ratio of silicon and iron is 0.1 ≦ (silicon / iron) <1, pH is less than 1, iron The concentration and pH are the following formula (1),
−0.14 × iron concentration (mass%) + 1.4> pH (1)
The iron-silica composite liquid is prepared by mixing so as to satisfy the above relationship.

  The ratio of silicon to iron is preferably lower in order to reduce the amount of sludge generated after using the flocculant. However, if the ratio is lower than 0.1, the effect of silica is reduced, and the finally obtained iron- The aggregation performance of the silica water treatment flocculant (hereinafter also simply referred to as flocculant) is deteriorated. On the other hand, in the case of 1 or more, the production method of the present invention is not applied, that is, iron-silica water that does not cause partial gelation during production and has excellent storage stability without adding an alkali described later. It is easy to obtain a processing aggregate.

  The ratio of silicon and iron can be easily adjusted by adjusting the concentration and mixing ratio of an aqueous solution containing an iron salt used as a raw material and an aqueous silicate solution.

  In the preparation of the iron-silica composite solution, it is extremely important that the iron concentration and pH satisfy the relationship of formula (1). As can be understood from the equation (1), the higher the iron concentration, the lower the pH of the composite solution. If the pH is higher (or the iron concentration is higher) than the range of the formula (1), gelation is likely to occur during the production of the iron-silica composite liquid, and it is difficult to produce it stably. If the pH at this point is 1 or more, it is difficult to produce an aggregating agent having a high iron concentration as intended by the present invention without causing gelation even if the production method of the present invention is adopted. (Conversely, when the iron concentration is low, the advantage of applying the present invention is small).

  In the production method of the present invention, the iron concentration of the iron-silica composite liquid is preferably in the range of 3 to 9% by mass (the lower limit of the iron concentration satisfying the above formula (1) is 2.9% by mass). Is). When the iron concentration is less than 3% by mass, it is relatively easy to produce an aggregating agent having a small silicon / iron molar ratio regardless of the production method of the present invention, and the production method of the present invention is applied. There is little meaning to do. On the other hand, when the iron concentration is extremely high, it is difficult to obtain storage stability for an industrially sufficient period even if alkali addition described later is performed to improve storage stability.

  The iron concentration can be adjusted by the concentration of the aqueous solution containing the iron salt and the ratio of use with other raw materials. The pH can be controlled by the type and amount of each raw material used. That is, as the amount of aqueous solution containing inorganic acid and iron salt (amount used and concentration) increases, the pH of the obtained iron-silica composite solution decreases. In order to stably produce the iron-silica composite liquid so as to satisfy the above formula (1), it is generally sufficient to use 1.1 equivalents or more of an inorganic acid with respect to the alkali component in the silicate aqueous solution. Preferably it is 1.1-1.2 equivalent. In the present invention, the pH is a value measured by a pH meter comprising a glass electrode and a reference electrode.

  The method for preparing the iron-silica mixed solution by mixing an aqueous solution containing an iron salt, an aqueous silicate solution, and an inorganic acid is not particularly limited, and a known method may be applied. Specifically, a silica sol is prepared by mixing an aqueous silicate solution and an inorganic acid, and an aqueous solution containing an iron salt is mixed therein, and an aqueous solution containing an iron salt and an inorganic acid are mixed in advance. And a method of mixing a silicate aqueous solution and the like. Examples of the mixing method include a method of adding a silicic acid aqueous solution to a mixed solution of an inorganic acid or an inorganic acid and an iron salt-containing solution, and collision at a speed of 5 m / second or more as described in Patent Document 1. The method of making it, etc. are mentioned. A method of mixing by collision is preferred because it has the advantage that partial gelation is less likely to occur and a large amount of iron-silica mixed solution can be rapidly produced.

In the present invention, the silica (SiO ₂ ) concentration at the time of preparing the iron-silica composite liquid is not particularly limited as long as it is in a range (0.3% by mass or more) that can satisfy the formula (1) and the like. At high concentrations, problems such as gelation tend to occur when preparing a silica sol from the above three components, so it is preferably 16% by mass or less. By adopting the above-described mixing by collision, a composite liquid having a high silica concentration of 10% by mass or more can be easily prepared.

  In addition, when a silica sol is prepared by mixing an aqueous solution of silicate and an inorganic acid and an aqueous solution containing an iron salt is used, it is preferable to age the silica sol before mixing the aqueous solution containing an iron salt. . As the aging method, it may be left still or may be gently stirred, and a known method may be appropriately employed. The viscosity reached by aging varies depending on the silica concentration, but the optimum relationship between silica concentration and viscosity is known. For example, when adopting a method of preparing a silica sol having a silica concentration of about 10 to 16% by collision mixing between an aqueous silicate solution and an inorganic acid as described in Patent Document 1, the viscosity is increased by aging. What is necessary is just to set it as about 6-30 mP * s.

  When a high-concentration silica sol is prepared by mixing an aqueous silicate solution and an inorganic acid as described above, it is preferably diluted before adding an alkali to be described later. This is because the final water treatment flocculant preferably has a silica concentration of 4% by mass or less. And when diluting after alkali addition, since there exists pH accompanying a density | concentration change, it is because it becomes comparatively difficult to adjust pH and an iron density | concentration in the range of Formula (2) mentioned later. The dilution may be before or after mixing the aqueous solution containing the iron salt, but is preferably before mixing the aqueous solution containing the iron salt in that a flocculant with better coagulation performance can be obtained.

  In the production method of the present invention, when dilution is performed after mixing all of the aqueous solution of silicate solution, inorganic acid and iron salt, the pH and iron concentration to be satisfied by the iron-silica composite solution are determined after dilution. It is the pH in the state before the alkali addition. Although the iron concentration and pH change when diluted, according to the study by the present inventors, the pH of a liquid containing such an iron component and silica sol in a concentrated manner is the pH change behavior of a simple acid dilute solution. In contrast, as shown in FIG. 1, when the equation (1) is normally satisfied before dilution, the equation (1) is also changed by dilution. In other words, the presence or absence of dilution after the addition of the iron salt aqueous solution usually does not affect whether the expression (1) is satisfied.

As the iron salt, the aqueous silicic acid solution and the inorganic acid, any known one can be used without any particular limitation. Specific examples of the iron salt include ferric chloride, ferric sulfate, and ferric nitrate. Moreover, as a silicic acid aqueous solution, a sodium silicate, potassium silicate, etc. can be used. As the inorganic acid, sulfuric acid, nitric acid, hydrochloric acid and the like can be used. As the iron salt, ferric chloride or ferric sulfate is preferable, and ferric chloride is particularly preferable. As the silicate aqueous solution, sodium silicate is preferable. When sodium silicate is used as a raw material, one having a molar ratio of SiO ₂ to Na ₂ O of 2.5 to 4.0 can be suitably used. As the inorganic acid, sulfuric acid is most preferable. The inorganic acid is preferably diluted with water as appropriate.

  These concentrations and amounts used may be appropriately adjusted so as to satisfy the above formula (1) and the like. For example, a silica sol is prepared by collision-mixing an aqueous silicate solution and an inorganic acid, and this contains an iron salt. When the method of mixing the aqueous solution is adopted, the silica aqueous solution having a silica concentration of 7 to 25% by mass is collided with the inorganic acid aqueous solution adjusted to 2 to 7N, and the 5 to 50% by mass iron salt aqueous solution is added thereto. The method of doing is mentioned.

In the present invention, an iron-silica mixed solution as described above is prepared, an alkali is added thereto, and the relationship between iron concentration and pH is expressed by the following formula (2).
−0.14 × iron concentration (mass%) + 1.4 <pH <−0.06 × iron concentration (mass%) + 1.2 (2)
The greatest feature is that the pH is adjusted to satisfy the above condition.

  Even when the amount of alkali added is small and the pH is lower than the above range, conversely, even when the amount of alkali added is too high and the pH becomes too high, good storage stability cannot be obtained.

  Even in a conventionally known method for producing an iron-silica water treatment flocculant, an iron-silica mixed solution satisfying the above formula (1) and the like was sometimes produced, but as in the present invention, an alkali was added thereto. No way has been done. As described above, this is presumed to be due to a known phenomenon in which an aqueous solution of iron salt such as ferric salt causes precipitation due to the addition of alkali.

  The amount of alkali added to make the relationship between the iron concentration and the pH within the above range may be confirmed experimentally. In general, among the inorganic acids used (although slightly affected by the amount of iron salt added), What is necessary is just to add the alkali of the quantity which can neutralize the acid amount with respect to the alkali component in silicate aqueous solution to 0.6-0.9 equivalent by a calculated value. Specifically, for example, when 1.1 equivalent of inorganic acid is used, 0.2 to 0.5 equivalent of alkali may be added.

  The type of alkali to be added is not particularly limited, but is preferably an alkali metal compound in that it hardly causes contamination of water to be treated. For example, alkali metal hydroxide, alkali metal carbonate, alkali metal Hydrogen carbonate and alkali metal oxides can be used. Among these, it is preferable to use sodium hydroxide or an aqueous sodium carbonate solution in view of handling and availability. The alkali to be used is preferably added to the iron-silica composite solution as an aqueous solution having an alkali metal compound concentration of 2 to 10% by weight.

  In the production method of the present invention, it is preferable to adjust the pH and the iron concentration of the iron-silica composite solution so that the pH is increased by 0.05 or more and the formula (2) is satisfied by the addition of the alkali. . In other words, when preparing an iron-silica composite liquid, it is preferable to adjust the compounding quantity of each component so that it may become pH lower. This is because if the iron-silica composite solution is prepared so as to have such a low pH, silica precipitation due to partial gelation at the time of this preparation is less likely to occur. On the other hand, since the concentration of iron or the like decreases due to the addition of alkali, it is preferable not to increase the amount of added alkali too much, so that the increase in pH due to the addition of alkali satisfies the formula (2) at 0.15 or less. It is preferable to prepare an iron-silica composite solution.

  In the present invention, the silica concentration in the water treatment flocculant composed of the iron-silica composite liquid is not particularly limited, but is preferably 0.3% by mass or more and 4% by mass or less, and 0.5% by mass. The above is more preferable. The higher the silica concentration is, the easier it is to increase the iron concentration, which is advantageous for storage and transportation. On the other hand, the storage stability tends to be relatively lowered. By making the silica concentration in the above range, it becomes easy to obtain a high iron concentration and better storage stability in a balanced manner. On the other hand, if the silica concentration is too low, a large amount of flocculant is required to secure a predetermined injection amount of iron concentration, and the storage and transportation costs become expensive.

  EXAMPLES Hereinafter, examples will be shown to describe the present invention more specifically, but the present invention is not limited to these examples.

(1) Description of Collision Mixing (Manufacturing Method of Iron-Silica Salt Composite Solution) In the examples and comparative examples shown below, the iron-silica salt composite solution was manufactured using the following apparatus. First, an iron-silica water treatment flocculant was produced in a Y-tube reactor as shown in FIG. The raw material supply pipe 4 is a sodium silicate aqueous solution having a diameter (inner diameter) of 1.4 mm × 10 mm in length of the throttle part, and the ferric chloride aqueous solution in the same way is 1.2 mm in diameter of the throttle part (inner diameter) × 10 mm in length. The iron-silica composite liquid was taken out from the discharge pipe 6 (tube diameter (inner diameter) 5 mm × length 30 mm). Each condition is shown in each example and comparative example.

  (2) Viscosity measurement: Measured at 30 ° C. using a tuning fork type vibration viscometer manufactured by A & D.

  (3) pH measurement: Measured at room temperature using a pH meter manufactured by Toa DKK Corporation.

  (4) Evaluation of flocculation performance: Kaolin (1000 degrees of turbidity standard solution for water quality test manufactured by Wako Pure Chemical Industries, Ltd.) was added to tap water, and a jar test was conducted using the turbidity adjusted to 20 as test water. Add 1000 mg of flocculant to 1000 mL of test water, add 5 mg of Fe, stir at a stirring speed of 150 rpm for 5 minutes, then stir at a stirring speed of 50 rpm for 10 minutes, and then stand still for 10 minutes. The performance of the obtained iron-silica water treatment flocculant for water treatment was examined by a method of collecting 50 ml and measuring turbidity.

Example 1
The sodium silicate aqueous solution used was a commercially available sodium silicate (SiO ₂ concentration 28 mass%, SiO ₂ / Na ₂ O molar ratio 3.15) diluted with water to obtain an SiO ₂ concentration 21.7 mass% aqueous solution. It was. The aqueous sulfuric acid solution used was an aqueous solution having a sulfuric acid concentration of 18% by mass diluted with 48% by mass with water. The flow rate of the sodium silicate aqueous solution was 1.0 L / min and the flow rate of the sulfuric acid aqueous solution was supplied to the Y-tube reactor at a flow rate of 0.81 L / min to obtain 5 L of silica sol solution in about 2 minutes 46 seconds. At this time, the flow rates of the sodium silicate aqueous solution and the sulfuric acid aqueous solution supplied to the reaction section were 10.8 m / s and 11.9 m / s, respectively.

The obtained silica sol had a SiO ₂ concentration of 13.0% by mass, and the silica sol had a pH of 1.48. 1 L of this silica sol was taken and aged for 120 minutes while gently stirring at 30 ° C. to obtain an aged silica sol having a viscosity of 10 mP · s.

200 ml (240 g) of this silica sol was taken, and 1050 g of water and 854 g of a 39.5% by mass ferric chloride aqueous solution were added. The pH of the iron-silica composite solution thus obtained was 0.58. While thoroughly stirring this solution, 100 ml of a 1.1N (44 g / L) aqueous sodium hydroxide solution was added over 10 minutes, and the SiO ₂ concentration was 1.4% by mass, the iron concentration was 5.2% by mass, and the moles of Si / Fe. 2246 g of an iron-silica composite solution having a ratio of 0.25 and a pH of 0.77 was obtained.

  When this agglomeration performance was evaluated using this iron-silica composite liquid as a water treatment flocculant, the supernatant water turbidity was 0.4, indicating good agglomeration performance. Moreover, when this water treatment flocculant was preserve | saved at room temperature and the storage stability was evaluated, this flocculant did not produce alterations, such as precipitation and gelation, for 60 days.

Examples 2 and 3 and Comparative Example 1
The amount of alkali added to the iron-silica composite solution obtained in Example 1 was changed to pH 0.71, pH 0.86, or pH 0.93, the SiO ₂ concentration was 1.4% by mass, and the iron concentration was 5.2% by mass. A flocculant composed of an iron-silica composite liquid having a Si / Fe molar ratio of 0.25 was obtained. Table 1 shows the storage stability of these flocculants.

Comparative Example 2
When the aggregation performance of the iron-silica composite solution having a pH of 0.58 before adding the aqueous sodium hydroxide solution in Example 1 was evaluated as it was, the supernatant water turbidity was 0.4. Moreover, as a result of evaluating the storage stability of this product, gelation occurred in 25 days.

  The storage stability evaluation results in Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1 together with the aggregation performance.

Example 4
To 200 ml (240 g) of the aged silica sol obtained in Example 1, 620 g of water and 854 g of 39.5% by mass ferric chloride aqueous solution were added. The pH of this iron-silica composite solution was 0.42. While thoroughly stirring this composite solution, 146 ml of 1.1N (44 g / L) aqueous sodium hydroxide solution was added over 15 minutes, and the SiO ₂ concentration was 1.7% by mass, the iron concentration was 6.2% by mass, 1863 g of an iron-silica composite solution having a molar ratio of 0.25 and a pH of 0.65 was obtained.

  When this agglomeration performance was evaluated using this iron-silica composite liquid as a water treatment flocculant, the supernatant water turbidity was 0.4, indicating good agglomeration performance. Moreover, when this water treatment flocculant was preserve | saved at room temperature and the storage stability was evaluated, this flocculant did not produce alterations, such as precipitation and gelation, for 25 days.

Examples 5 and 6 and Comparative Example 3
The amount of alkali added to the iron-silica composite solution obtained in Example 4 was changed to pH 0.56, pH 0.78 or pH 0.85, and the SiO ₂ concentration was 1.7% by mass and the iron concentration was 6.3% by mass. A flocculant composed of an iron-silica composite liquid having a Si / Fe molar ratio of 0.25 was obtained. The stability of these flocculants is shown in Table 2.

Comparative Example 4
When the storage stability of the iron-silica composite solution having a pH of 0.42 before adding the sodium hydroxide aqueous solution in Example 4 was evaluated, gelation occurred in 9 days.

  The storage stability evaluation results in Examples 4 to 6 and Comparative Examples 3 and 4 are shown in Table 2 together with the aggregation performance and the like.

Example 7
To 200 ml (240 g) of the aged silica sol obtained in Example 1, 1680 g of water and 854 g of 39.5% by mass ferric chloride aqueous solution were added. The pH of this iron-silica composite solution was 0.79. While thoroughly stirring this composite solution, 73 ml of 1.1N (44 g / L) aqueous sodium hydroxide solution was added over 7 minutes, and the SiO2 concentration was 1.1% by mass, the iron concentration was 4.1% by mass, and the moles of Si / Fe. 2848 g of an iron-silica composite solution having a ratio of 0.25 and a pH of 0.90 was obtained.

  When this agglomeration performance was evaluated using this iron-silica composite liquid as a water treatment flocculant, the supernatant water turbidity was 0.5, indicating good agglomeration performance. Moreover, when this water treatment flocculant was preserve | saved at room temperature and the storage stability was evaluated, this flocculant did not produce alterations, such as precipitation and gelation, for 110 days.

Examples 8 and 9 and Comparative Example 5
The amount of alkali added to the iron-silica composite solution obtained in Example 7 was changed to pH 0.86, pH 0.94 or pH 1.00, SiO ₂ concentration 1.1 mass%, iron concentration 3.9 mass%. A flocculant composed of an iron-silica composite liquid having a Si / Fe molar ratio of 0.25 was obtained. Table 3 shows the storage stability of these flocculants.

Comparative Example 5
When the storage stability of the iron-silica composite solution having a pH of 0.79 before addition of the aqueous sodium hydroxide solution in Example 7 was evaluated, gelation occurred in 60 days.

  The storage stability evaluation results in Examples 7 to 9 and Comparative Examples 5 and 6 are shown in Table 3 together with the aggregation performance and the like.

Example 10
To 200 ml (240 g) of the aged silica sol obtained in Example 1, 250 g of water and 810 g of a 39.5 mass% ferric chloride aqueous solution were added. The pH of this iron-silica composite solution was 0.25. While thoroughly stirring this composite liquid, 205 ml of 1.1N (44 g / L) aqueous sodium hydroxide solution was added over 20 minutes, and the SiO2 concentration was 2.0% by mass, the iron concentration was 7.5% by mass, and the Si / Fe mol. 1553 g of an iron-silica composite solution having a ratio of 0.25 and pH of 0.45 was obtained.

  When this agglomeration performance was evaluated using this iron-silica composite liquid as a water treatment flocculant, the supernatant water turbidity was 0.5, indicating good agglomeration performance. Moreover, when this water treatment flocculant was preserve | saved at room temperature and the storage stability was evaluated, this flocculant did not produce alterations, such as precipitation and gelation, for 11 days.

Examples 11 and 12
The amount of alkali added to the iron-silica composite solution obtained in Example 10 was changed to pH 0.40 or pH 0.66, SiO ₂ concentration 2.1 mass%, iron concentration 7.6 mass%, Si / Fe A flocculant composed of an iron-silica composite liquid having a molar ratio of 0.25 was obtained. Table 4 shows the storage stability of these flocculants.

Comparative Example 7
When the storage stability of the iron-silica composite solution having a pH of 0.25 before the addition of the aqueous sodium hydroxide solution in Example 10 was evaluated, gelation occurred in 2 days.

  The storage stability evaluation results in Examples 10 to 12 and Comparative Example 7 are shown in Table 4 together with the aggregation performance and the like.

Example 13
To 200 ml (240 g) of the aged silica sol obtained in Example 1, 440 g of water and 427 g of a 39.5 mass% ferric chloride aqueous solution were added. The pH of this iron-silica salt composite solution was 0.56. While thoroughly stirring this solution, 105 ml of an aqueous 1.1N (44 g / L) sodium carbonate solution was added over 10 minutes. The SiO ₂ concentration was 2.6% by mass, the iron concentration was 4.8% by mass, and the Si / Fe molar ratio. 1214 g of 0.5-pH 0.85 iron-silica salt composite solution was obtained.

  When this agglomeration performance was evaluated using this iron-silica composite liquid as a water treatment flocculant, the supernatant water turbidity was 0.3, indicating good agglomeration performance. Moreover, when this water treatment flocculant was preserve | saved at room temperature and the storage stability was evaluated, this flocculant did not produce alterations, such as precipitation and gelation, for 12 days.

Comparative Example 8
The amount of alkali added to the iron-silica composite solution obtained in Example 13 was changed to pH 1.00, the SiO ₂ concentration was 2.6% by mass, the iron concentration was 4.8% by mass, and the Si / Fe molar ratio was 0. A flocculant composed of .25 iron-silica composite liquid was obtained. Table 5 shows the storage stability of this flocculant.

Comparative Example 9
When the storage stability of the iron-silica composite solution having a pH of 0.56 before addition of sodium carbonate in Example 13 was evaluated, gelation occurred in 4 days.

  The storage stability evaluation results in Example 13 and Comparative Examples 8 and 9 are shown in Table 5 together with the aggregation performance and the like.

  In the above experimental results, the example in which the time until gelation or the like is caused by addition of alkali is 1.5 times longer than that in the case where no alkali is added, is A comparative example was not obtained. These results are plotted in FIG. From this figure, it can be seen that the effect is obtained in the case where the formula (2) is satisfied by the addition of alkali.

  As can be understood from the comparison of Examples 1, 4, 7, and 10 or Comparative Examples 2, 4, 6, and 7, the storage stability tends to improve as the concentration decreases. However, for example, in Example 10, where the concentration is higher, the time until gelation is longer than in Comparative Example 4, so that high storage stability exceeding the effect of concentration is obtained by satisfying Equation (2). Can do. It is clear that a higher concentration of the flocculant is advantageous in terms of storage and transportation, and the present invention is an excellent technique having such advantages.

FIG. 1 is a plot of the relationship between iron concentration and pH in Comparative Examples 2, 4, 6, and 7. In all these comparative examples, the same amount of 39.5% by mass ferric chloride aqueous solution was added to 240 g of the iron-silica composite solution having a SiO ₂ concentration of 13.0% by mass produced in Example 1. The only difference is the amount of water added with the aqueous ferric chloride solution. That is, these comparative examples are experimental results with different degrees of dilution with water.

  As can be understood from this figure, an iron-silica composite prepared by blending predetermined amounts of an aqueous silicate solution, an inorganic acid and an aqueous iron salt solution to satisfy Formula (1) (and not satisfy Formula (2)). If the solution is simply diluted with water and the concentration is changed, the relationship between the iron concentration and the pH satisfying the formula (2) is not obtained.

Comparative Example 10
In order to produce an aggregating agent that directly satisfies the formula (2) without adding an alkali, an experiment was conducted by reducing the amount of sulfuric acid used by an amount corresponding to the amount of alkali added. That is, in Example 1, the silica sol was manufactured by colliding with sodium silicate at a flow rate of sulfuric acid of 0.63 L / min. As a result, many silica gels were present in the obtained silica sol solution, and a good silica sol solution could not be obtained.

The figure which shows pH change at the time of diluting an iron-silica composite liquid with neutral water. The schematic diagram of the Y-tube reaction apparatus for manufacturing an iron-silica composite liquid. The figure which shows the relationship between the iron concentration in an iron-silica composite liquid, pH, and storage stability.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Storage tank of inorganic acid 2 Storage tank of silicate aqueous solution 3 Y-shaped reactor 4 Raw material supply pipe 4 'Raw material supply pipe 5 Reactor 6 Discharge pipe

Claims (5)

An aqueous solution containing an iron salt, an aqueous silicate solution, and an inorganic acid are mixed, and the ratio of silicon and iron is 0.1 ≦ (silicon / iron) <1, the pH is less than 1, the iron concentration and pH are as follows. Formula (1),
−0.14 × iron concentration (mass%) + 1.4> pH (1)
An iron-silica composite solution satisfying the above relationship is prepared, then an alkali is added to the composite solution, and the relationship between iron concentration and pH is expressed by the following formula (2).
−0.14 × iron concentration (mass%) + 1.4 <pH <−0.06 × iron concentration (mass%) + 1.2 (2)
PH is adjusted so as to satisfy the following conditions: water treatment aggregation comprising an iron-silica composite liquid in which the ratio of silicon and iron is in the range of 0.1 ≦ (silicon / iron) <1 in molar ratio Manufacturing method.   The method for producing an aggregating agent for water treatment according to claim 1, wherein the iron concentration after adjusting the pH by adding an alkali is in the range of 3 to 9% by mass.   The aqueous solution containing an iron salt, an aqueous silicate solution, and an inorganic acid are mixed so that the iron concentration of the iron-silica composite solution before adding the alkali is in the range of more than 3% by mass and 10% by mass or less. 2. A method for producing a flocculant for water treatment according to 2. The method for producing a flocculant for water treatment according to any one of claims 1 to 3 , wherein an increase in pH by adding an alkali is at least 0.05 or more.
The ratio of silicon and iron obtained by mixing an aqueous solution containing an iron salt, an aqueous silicate solution, and an inorganic acid is 0.1 ≦ (silicon / iron) <1, in molar ratio, pH is less than 1, and the iron concentration is 3 mass% or more, iron concentration and pH are the following formula (1),
−0.14 × iron concentration (mass%) + 1.4> pH
The relationship between the iron concentration and pH is represented by the following formula (2) by adding an alkali to the water treatment flocculant composed of an iron-silica composite liquid in the range of
−0.14 × iron concentration (mass%) + 1.4 <pH <−0.06 × iron concentration (mass%) + 1.2
PH is adjusted so as to satisfy the following conditions: water treatment aggregation comprising an iron-silica composite liquid in which the ratio of silicon and iron is in the range of 0.1 ≦ (silicon / iron) <1 in molar ratio Agent stabilization method.

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