JPS60145100A - Purification of sugar solution - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] It is about law.

Conventionally, in order to purify a sucrose solution such as spinel sucrose, it is common to go through the steps shown below.

Zunaichi first washes the raw sugar to remove impurities adhering to the surface, and then dissolves the sugar after pre-canting in water and water to make a raw sugar solution. Lime, Q and carbonate scum are added to the raw sugar solution, and the resulting calcium carbonate is treated with chemicals such as carbonation, which adsorbs and removes impurities such as suspended solids and pigment components. The bone char is treated to remove residual impurities, especially pigment components, and then passed through a layer of granular ion exchange resin for decolorization or decolorization and desalting to obtain a purified sucrose solution. in this way,
In the conventional 1 blue production process, pigment components contained in a sucrose solution with a high color value are removed/rice is subjected to adsorption treatment using activated carbon or bone char, and adsorption treatment using a granular ion exchange resin layer. things are being done.

By the way, when adsorption treatment is performed using activated carbon or charcoal as described above, running costs are high because the adsorption capacity of these activated carbons and bone charcoal is 100%, so it is impossible to use a considerable amount while supplementing light. If the process becomes too large, extra steps such as deashing and filtration steps may become necessary, making the process complicated and reducing productivity.

On the other hand, in the purification process using the above-mentioned granular ion exchange resin, the mass flow capacity decreases due to factors such as a decrease in exchange capacity and a decrease in intraparticle diffusion rate due to organic contamination where organic substances are irreversibly adsorbed on the particle surface. Due to a decrease in the purity of the liquid, the granular ion exchange resin is replaced with a new one at some point, and the used resin is discarded as industrial waste. Therefore, since the granular ion exchange resin is expensive, the peeling increases the running cost, and the disposal of the used resin, which is industrial waste, has become a problem from the viewpoint of pollution.

As described above, in the conventional method for purifying a sucrose solution, there is a lot of waste when viewed as an industrial scale system, and this result is reflected in the cost of the product.

Therefore, the inventors of the present invention have repeatedly carried out the W1 test to simplify the sucrose solution purification system and make effective use of industrial waste. Kokichi has superior dye adsorption ability and is recyclable. Therefore, Kokichi can effectively purify a sucrose solution after carbonation saturation by carrying out two-stage adsorption of a powdered anion exchange resin and a granular ion exchange resin. What can be done: It is possible to crush granular anion exchange resin with reduced capacity and reuse it as powdered anion exchange resin.It is also possible to use recycled waste liquid from granular ion exchange resin as a regenerating agent for powdered anion exchange resin. We have come to the conclusion that this is the case.

The present invention has been made based on the above-mentioned knowledge, and the first invention includes a decoloring step in which a sucrose acid solution is brought into contact with a powdered anion exchange resin to remove an adsorbed substance having a medium rQ dye. The powdered anion exchange resin used in the above decolorization step is a purification process in which it is brought into contact with a granular ion exchange resin mainly composed of a strongly basic anion exchange resin. The second invention is characterized in that it can be used repeatedly by contacting with the ion-containing 1d solution to desorb the adsorbed substance, and the second invention is to apply the sucrose solution I to powdered anion exchange resin. The decolorization process consists of a decolorization step in which adsorbed substances with a dye as the medium are removed by contacting with the dye, and a purification step in which the adsorbed substance is brought into contact with a granular ion exchange resin mainly composed of a strongly basic anion exchange resin. The powdered anion exchange resin used is the powdered anion exchange resin A produced by crushing the granular ion exchange resin used in the purification step 2, and the powdered anion exchange resin is treated with an acid and/or Alternatively, the invention is characterized in that it can be regenerated and used repeatedly by contacting it with a metal ion-containing solution to desorb the adsorbed substance, and the third invention is characterized in that the sucrose solution is brought into contact with a powdered anion exchange resin. The process consists of a decolorization step in which the adsorbed substances, mainly dyes, are removed, and a purification step in which the powdered anions used in the decolorization step are brought into contact with a granular ion exchange resin mainly consisting of a strongly basic anion exchange resin. The exchange resin is a powdered anion exchange resin manufactured by pulverizing the granular ion exchange resin used in the above purification process, and this powdered anion exchange resin is used as a recycled waste of the granular ion exchange resin used in the above purification process. It is characterized in that it can be regenerated and used repeatedly by bringing it into contact with a liquid and desorbing the adsorbed substance.

Hereinafter, an example of an embodiment of the present invention will be explained from ls with reference to a frame not shown in FIG.

In this example, firstly, raw sugar is washed using the usual method in sugar step 1, the impurities adhering to the surface of the raw sugar are washed off, and then Ino 111 is dissolved in the usual method in d-lysis step 2. jlpi L, produce a raw sugar solution.

4I゛Since the present invention includes a decolorization step that strongly adsorbs the pigment components using a powdered anion exchange resin, which will be described later, in some cases, the sugar washing step 1 may be omitted altogether. Alternatively, the usage notification of washing water can be significantly reduced.

Next, a chemical treatment step 3 in which a chemical that produces a precipitate is added to the crude sugar solution obtained in the dissolution step 2, and impurities such as suspension and pigment components are adsorbed and removed by the precipitate. Implement. The chemical treatment step 3 involves the treatment of raw sugar m
Calcium phosphate is produced by adding lime and carbonic acid scum to the solution and reacting the two to generate calcium carbonate, which adsorbs and removes the impurities, or by adding lime and phosphoric acid to the raw sugar solution and allowing the two to react. So-called phosphoric acid clarification, in which the impurities are adsorbed and removed, or lime and carbonate scum are first added to a raw sugar solution, and the two are reacted, the resulting calcium carbonate adsorbs and removes the impurities, and then lime and phosphoric acid are added. (If lime is left in the reaction, only phosphoric acid is added) Various methods such as carbonation saturation and phosphoric acid clarification combined treatment in which the impurities are further adsorbed to the phosphoric acid produced There is, but
The point is to add a chemical that produces a precipitate, but any treatment that involves adding an adsorbent such as magnesium oxide or nitride to adsorb and co-precipitate the impurities in the crude sugar syneresis to the precipitate will not work. It may be a process, and it is preferable to select the most suitable process depending on the situation.

Next, the precipitate generated in the chemical treatment step 3 is filtered, and the filtrate is used in the decolorization step 4 using a powdered anion exchange resin.
The remaining dye components are adsorbed by passing the liquid through an adsorption tower filled with the powdered anion exchange resin. In addition, in this decolorization step 4, if the I) I-1 of the sugar solution is high due to the addition of macanenium oxide, etc. in the previous chemical treatment step 3, powdered cation exchange resin in the form of 1-1 is used. It is also effective to use them together. According to experiments conducted by the present inventors, it is sufficient to use pulverized used granular cation exchange resin as the powdered cation exchange resin, and at the same time when regenerating the powdered anion exchange resin described later. It turns out that it can be regenerated.

1. The powdered anion exchange resin used in the decolorization step 4 is a copolymer of Sunareno and vinylbenzene or a copolymer of acrylic and novinylbenzene. Strongly basic anion exchange resins having ionic substituents such as strong basic groups such as primary amine groups, secondary amine groups, primary amine groups, and polyamine groups, medium basic groups, and weak basic groups; Examples include basic anion exchange resins and weakly basic anion exchange resins, and their ionic forms include OII, C7l, and S.
Various salt forms such as O4 form are mentioned, but especially C
I-type strongly basic anion conversion resins are the most effective.

The particle size of the powdered anion exchange resin is as follows.

It is preferably 250 μm or less, more preferably 100 μηL or less. If the above particle size is 250/1 full or more, the adsorbed substance containing the pigment component will be difficult to desorb, making it difficult to regenerate. In addition, if the particle size of the powdered ion exchange resin is 5 μm or less, especially 1.5 μm or less, which has a high risk of leakage, it will be difficult to separate, and there is a risk that the resin will be mixed into the processing solution. There is.

Methods for producing the powdered anion exchange resin include a method of pulverizing a granular anion exchange resin and a method of industrial synthesis, but pulverization is generally used. In addition, the pulverization methods include air flow pulverization method, freeze pulverization method,
Mechanical pulverization methods may be used, but it is particularly preferable to use a pneumatic pulverization method or a freeze pulverization method.

The above-mentioned pneumatic pulverization method is a method in which the particulate anion exchange resin, which is a raw material, is self-pulverized into fine particles by vibrations caused by high-frequency pressure fluctuations caused by high-speed vortex flow of air.
It has the characteristic that the time required to powder it to 0 μnL or less is extremely short (about several seconds). This pulverization method causes the temperature rise during pulverization to be less than 40°C, so there is no deterioration of the resin due to heat.What is more distinctive about this powder is that it has excellent desorption properties for pigment components and has a large regeneration effect. An anion exchange resin having a similar shape can be obtained.

In addition, in the self-freeze pulverization method, granular anion exchange resin is brought into direct contact with, for example, liquid nitrogen, cooled to below -100°C, and then the cooled anion exchange resin is immediately placed in a hammer mill. etc. to powder it. In addition,
Refrigerants that can be used for the above cooling include, in addition to the liquid nitrogen mentioned above, various low-boiling point liquefied scum such as liquid carbon dioxide, liquid oxygen, and liquefied propane. It is preferable to use liquid chlorine.

In this case as well, the grain size is fine and there is no thermal deterioration.
Moreover, a powdered anion exchange resin having a relatively uniform particle size can be obtained.

On the other hand, in the mechanical pulverization method using a ball mill or hammer mill, it is difficult to make the particle size of the pulverized product uniform, and when using the obtained powdered anion exchange resin, it is necessary to use a sieve etc. to It is preferable to use them selectively. Furthermore, in the above mechanical pulverization method, the time required for pulverization is long and the temperature rise is large, so there is a risk that the decolorizing performance of the powdered anion exchange resin will be reduced.

The anion exchange resin has a relatively low thermal temperature, for example, an anion exchange resin whose ion exchange group is a quaternary ammonium group.
The maximum operating temperature of strongly basic anion exchange resin is 60°C.
It is said that when the temperature exceeds this temperature, thermal decomposition of the ion exchange group occurs rapidly. Although the details of the adsorption mechanism of the dye component by the anion exchange resin are unknown, it is thought that the polarity of the anion exchange resin particle surface is largely involved, so it is preferable to apply heat during the crushing. do not have.

The above-mentioned powdered anion exchange resin has better performance than bone char or granular activated carbon in terms of decolorizing effect, and the purpose can be achieved in a light amount using an amount of 0.5 h per solution. moreover,
This usage amount can be significantly reduced by adopting a multi-stage contact method or a powder resin layer method. For example, as shown in FIG.
] Efficient treatment is possible by adopting the Mary-Coulant method in which the tower is a ladle tower and regeneration operations are performed sequentially. In this case, the amount of solution purified per unit amount of resin increases significantly, and in particular, in the powder resin layer method, the amount reaches about 10 times that of the conventional method using a granular anion exchange resin. In addition, when creating the above-mentioned powdery resin layer, a powdery anion exchange resin, /r isotonic earth, a fibrous filter aid, etc. may be mixed and used.

In addition, when using a powdered anion exchange resin, the liquid to be treated has a color index A I (Attenuation
70J) can be most effectively decolorized when it is a high color value solution of 100 or more.

6 Furthermore, the above-mentioned powdered anion exchange resin does not simply have a higher adsorption amount than the granular anion exchange resin;
It was found that the amount of adsorption is specifically large for polymeric dyes having absorbance characteristics in the visible high wavelength region of 60 to 720 nm.

On the other hand, if the decolorizing ability of the powdered anion exchange resin has decreased, in the regeneration step 5, an acid and/or metal ion-containing solution is used as a regenerant, and the dye component is brought into contact with the regenerant using, for example, a hatch method. The adsorbed substances are desorbed, regenerated, and used again to decolorize the solution. Note that during the above regeneration (B), it may be effective to use ultrasonic stirring in combination in order to improve the separation of colloidal components attached to the surface of the powdered anion exchange resin. Some acid and/or metal ion containing solutions include:
Acid-containing organic solvents or metal ion-containing organic solvents are effective, especially acid-containing acetone, acid-containing methanol,
Methanol containing alkali metal ions is effective. In addition, when a commercial solvent such as ethanol, ether, chloroform, .\xa7, etc. is used as the above-mentioned organic solvent, there is also an effect of desorbing the dye component. In addition, as the above acid (,
Examples include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, etc., but it is more effective to use mineral acids such as hydrochloric acid. In addition, as a metal ion-free solution, edible water, hydroxide]・
The use of lithium-containing saline, hydrochloric acid-containing saline, etc. is also effective, but its regeneration effect is inferior to that of the acid-containing acetone and the like.

Most preferably, it is first brought into contact with an aqueous solution containing an acid and/or a metal ion, and then brought into contact with an organic solvent containing an acid and/or a metal ion.

By the way, regarding the acid concentration in the above acid-containing inorganic solvent,
The higher the concentration, the faster the desorption rate, but even when the concentration was increased by more than 5%, the amount of desorption did not increase significantly. Also,
When acid-containing acetone was used, no difference was observed in the desorption performance even though the water content in the acetone was around 50%.

When regenerating the powdered anion exchange resin described in Section 2 using a regenerating agent containing a highly permeable organic solvent such as acetic acid, the rate of desorption is very fast, and contact with the resin for a short period of time is difficult. It is possible to almost completely desorb the adsorbed dye components. In addition, if an aqueous solution is used as the regenerant in item 1, it is necessary to use a large amount of the regenerant, and the conditions for use must be at high temperatures, or the regenerant mainly consists of an organic solvent. When used, the amount used can be significantly reduced, and usually 10 to 20 times the amount of the powdered anion exchange resin to be regenerated is sufficient. and,
When using a regenerating agent mainly composed of the above-mentioned organic solvent, the organic solvent used for regeneration can be easily recovered and reused by distillation, etc., and the amount of waste liquid can be reduced, etc. The benefits are significant. Furthermore, when recovering the above-mentioned organic solvent, there is also the effect of facilitating the recovery of valuable substances in the waste liquid.

The sucrose droplets from which most of the pigment components have been removed in the decolorization step 4 described above are further sent to a purification step 6 using a granular ion exchange resin to remove remaining pigment components, salts, and the like.

The granular ion exchange resin used in the purification step 6 of 1. is generally OYElrr with a particle size of 0.3 to Q, and its types include strongly basic anion exchange resins, weakly basic anion exchange resins, etc. Examples include exchange resins, strongly acidic cation exchange, 1-one father exchange + DA fat, weak acid cation exchange (also 1 fat, etc.), and one example is a strong basic anion exchange resin tower 12, weak The acidic cation exchange resin tower 13 and the weakly basic anion exchange resin tower 14 (usually omitted) can be passed through the Perth method, or a strong basic anion exchange resin and a strong acid cation exchange resin as shown in Figure 4 can be used. The sucrose solution is purified to a high degree of purity by a modified reverse method (MAK) in which the liquid is sequentially passed through an ion exchange resin mixing tower 15, a strong basic anion exchange resin tower 16, and a weak acid cation exchange resin tower 17. It is also effective.

When the capacity of the above granular ion exchange resin decreases, in the regeneration step 7, a regenerating agent such as an alkaline solution such as a sodium hydroxide solution, an acid such as hydrochloric acid, or a salt d solution such as a thorium chloride solution is passed through the resin. In addition, since the liquid to be treated that is supplied to the purification step 6 has had its pigment components strongly removed by the powdered anion exchange resin in the decolorization step 4, the granular It can effectively prevent contamination of the ion exchange resin and considerably extend its service life.

The sucrose solution can be purified to a high degree of purity by passing through the decolorization step 4 and the purification step 6 described above, and a fine liquor can be obtained.

The method described above can simplify the equipment, reduce the running cost of auxiliary materials such as washing water, simplify operation management, etc., and can also increase the liquid flow rate by 10 times compared to normal systems. Since it is possible to do more than that, the economic effect is significant.

By the way, the performance of the granular ion exchange resin used in the purification step 6 gradually decreases after long-term use, and eventually it becomes impossible to restore the performance to the original level even by regeneration. In this case, the used particulate ion exchange resin is generally disposed of as industrial waste, but in the present invention it is possible to reuse it.

That is, as shown in FIG. 5, the granular ion exchange resin that has become unusable in the purification step 6 is pulverized in the pulverization step 8, and further brought into contact with a regenerating agent in the regeneration step 9 to be regenerated, and then processed in the decolorization step. It is possible to use it as a powdered ion exchange resin (No. 4).

Examples of the method for pulverizing the granular ion exchange resin include the air flow pulverization method and freeze pulverization method as described above, and the regeneration agent used in the regeneration step 9 includes the above-mentioned regeneration of the powdered anion exchange resin. Acid- and/or metal ion-containing solutions may be used as well as regenerants that are sometimes used.

Through the above-mentioned pulverization process 8 and regeneration process 9, the adsorbed substances accumulated in the resin pores of the used granular io7-converted persimmon fat, especially colloidal components containing polymeric dyes and heavy metals, are easily removed, resulting in a new product. A similar powdered ion exchange resin is obtained.

In this way, in the present invention, the used granular ion exchanger 111 fat, which is originally discarded, is pretreated.
The decolorization process 4-c can be reused as if it were new, and when these decolorization process 4 and purification process 6 are considered as a series of systems, the economic benefits are extremely large.

Furthermore, in the present invention, it is even possible to reuse the regeneration waste liquid used for regenerating the granular ion exchange resin in the purification step 6.

That is, as shown in FIG. 6, the recycled waste liquid used for regenerating the granular ion exchange resin in the purification step 6 is hardly contaminated even after the granular ion exchange resin is treated with the sucrose solution, so that the regenerated liquid used in the refining step 6 is not contaminated with the powder in the decolorization step 4. It becomes possible to reuse the anion exchange resin ψ by using it as a regenerating agent. Therefore, it is advantageous not only economically, but also in terms of water treatment, etc., since the amount of waste liquid is reduced.

Next, specific examples will be described in order to make the present invention more clear, but it goes without saying that the present invention is not limited to these examples.

Example 1 Powdered resin (average particle size 18.5μ) made from granular anion exchange resin used in a sugar refinery by air-pulverization method (average particle size 18.5μ)
(moisture 51.5%) 1g and 2 to 5 liters of Noj Ruswool
A powdered resin column was prepared by mixing the mixture with 05 J of superaid agent, which had been prepared by cutting it into a length of 1 tl++, and filling it in a carat with a diameter of 2 onb and a height of 10 atb.

Four series of the above powdered resin columns were prepared, and the three towers constituted a three-stage decolorization system using the Mary Colant method, and the effluent was passed through at a rate of 40 nd' per hour. The remaining θ4 column is used as a regeneration column and is used as a regeneration column for every 5 mL of powder resin column processed.
Regeneration operation was carried out by passing 2 mL of Ce-containing 80% acetic acid-7 water (Jml) at a rate of 40ml per hour, and then washing by passing 40+n/water at a rate of 8Qml per hour. The time required for regeneration was approximately 1 hour.

Next, the sucrose solution treated with the above three-stage decolorization system was mixed with 2Q ml of a hydroxyl group-type strongly basic anionic father exchange resin and Na
M tower formed by mixing and filling ml of strongly acidic cation exchange resin IQ, hydroxyl group type strongly basic anion exchange resin IQ
A tower packed with trtl, weakly acidic cation exchange resin 20
4 (Jml) per hour at a temperature of 50"C.
It passed at a rate of .

Table 1 shows the quality of the sucrose solution in each step.

1st Surface Charcoal f Definition In this example, the amount of sucrose solution processed for the powdered anion exchange resin reached 500 times the resin volume, and the liquid passing rate was extremely high at S, V, (space velocity) of 40. It was found that both values were more than 10 times larger than those of the normal system.

Example 2 Raw sugar (produced in the Philippines, ash content 0.45%, color value [,1
), Ll, 650 U, invert sugar R,S, 0.7%
) ':i: Water? l After dissolving, carry out the carbonation saturation method and δ
A clear liquid was obtained after 5 filtration. The volume of this clear liquid is 13L.

A powdered anion exchange resin (
Water 51.5%) 10& Powdered weakly acidic cation exchange resin (H type, water 47%) for removing alkaline components
After adding li and reacting with stirring for 30 minutes at a temperature of 70°C, it was separated by r using 1 paper (/l62) and P′o, CL-1
I got it.

Next, this P liquid cL-1 was mixed with powdered anion exchange resin (
Mix 2g of water (51.5%) with crow wool and make a diameter of 2o.
The liquid was passed through a powdered resin column packed in a column of nb and height 10 at S, V, 40 to obtain treated sugar solution CL-2.

Sara (Otsu type 01-1 strong base anion exchange resin, Na
The above-mentioned treated sugar solution EL, -2 was added to the improved reverse method Od production process consisting of a strongly acidic cation exchange resin and a weakly acidic cation exchange resin. The treated sugar solution was designated as CL-3.

In addition, the powdered anion exchange resin added to the clarified liquid BL was added to the regenerated effluent (NaCe-containing H
Although most of the adsorbed dye was desorbed by contact treatment with the containing solution C1 (a Cl-containing Na, OH solution), in order to make the regeneration operation more complete, further contact was performed using 59 ml of an acetone solution containing 5% L-IC4. Processed. In addition, through this regeneration operation, the powdered weakly acidic cation exchange resin was also ion-exchanged into the H form, making it possible to reuse it.

Table 2 shows the quality of each sugar solution after repeated use for 5 cycles.

Table 2

[Brief explanation of the drawing]

FIG. 1 is a flowchart 1 showing an example of an embodiment of a real gun according to the present invention.
・Figure 2 is a schematic diagram showing an example of a specific configuration of the decolorization process, Figure 3 is a schematic diagram showing an example of a specific configuration of the purification process, and Figure 4 is a schematic diagram showing another example of the purification process. It is a diagram.
- FIG. 5 is a flow chart showing another example of an embodiment of the invention.
1, and the stripe diagram 6 shows still another example.

Claims (1)

[Claims] (1) Sei (),! ! A decolorization step in which the solution is brought into contact with a powdered anion exchange resin to remove the dye, and a purification step in which a strongly basic anion exchange resin is brought into contact with a granular ion exchange resin. It consists of -
The powdered anion exchange resin used in the decolorization step forms keratosis when it comes into contact with an acid and/or metal ion-containing solution to desorb the adsorbed substance, making it a sucrose solution that is recommended for repeated use. Purification method. (Decolorization step to remove the adsorbed substance (b) by contacting the 2-ton sucrose solution with the powdered anion exchange resin to remove the pigment) and contacting the granular ion conversion resin, which is mainly made of a strongly basic anion exchange resin. The powdered anion exchange resin used in the decolorization step is a powdered anion exchange resin produced by pulverizing the granular ion exchange resin used in the purification step, and the powdered anion exchange resin is A method for purifying a sucrose solution, which comprises bringing an ion exchange resin into contact with an acid and/or metal ion-containing solution to desorb adsorbed substances, thereby regenerating and repeatedly using the resin. (3) a decoloring step in which the sucrose solution is brought into contact with a powdered anion exchange resin to remove the adsorbed substance containing the dye;
It consists of a purification step in which the powdered anion exchange resin used in the decolorization step is brought into contact with a granular ion exchange resin mainly composed of a strongly basic anion exchange resin. The produced powdered anion exchange resin is regenerated and repeatedly used by contacting the powdered anion exchange resin with the regenerated waste liquid of the granular ion exchange resin used in the above purification process to desorb the adsorbed substances. A method for purifying a sucrose solution, characterized by: