JPH0655160B2 - Method for decolorizing and desalting molasses - Google Patents

Description

TECHNICAL FIELD The present invention relates to a highly efficient and highly decolorizing desalination purification method for molasses in the middle of the manufacturing process of a sugar factory or waste molasses, and more specifically to molasses containing water and water. Calcium oxide is added to adjust the concentration and alkali, and after heating to 55 to 65 ° C, ethyl alcohol is added to this to form a coagulated precipitate in the high alcohol content, and then sedimentation and centrifugation. , Or after deagglomeration and clarification by removing the agglomerates by over-operation, etc., carbon dioxide gas is filled to pass through the formed calcium carbonate to soften and readjust the pH to the neutral range, and then multiplex. The effect can or pervaporation type alcohol membrane separation and concentration device, or the combination of ultrasonic vibration type alcohol separation and concentration device and multiple effect can separates and concentrates alcohol for recycling and reuse, while molasses Residual polymer dyes are separated by ultra-permeation membrane or negatively charged polymer reverse osmosis composite membrane showing permeability in loose RO region. Separated dyes, rubbery substances, etc. are mixed with alcohol in the first step. By recycling into the process, while removing and reaggregating and solidifying and separating the pigment components, the system recovers only sugars while preventing loss of sugars to the outside of the system, and achieves a high decolorization rate of 95% or more, The present invention relates to a method for highly destaining and desalting and refining molasses, characterized by performing final destaining with a small amount of activated carbon, synthetic adsorption resin or the like as it is, and further with desalting with an electrodialysis device.

(Prior art) Sugar production from sugar cane, sugar beet, or molasses, which is a mother liquor for separating sugar crystals in the purification of sugar as a raw material, is usually performed three times or more until sugar crystals can be economically crystallized and recovered. It is obtained by repeating decoction and separating the decoction over a number of times.Usually, when such an operation is repeated a plurality of times, the sugar content in molasses gradually decreases, while pigments other than sucrose, inorganic salts, and polysaccharides. , Rubber substances, reducing sugars, proteins, etc. are concentrated, and after the sugar recovery operation by decoction has reached the economical limit, it is discharged to the outside of the process system. 30% inside and outside,
When reducing sugars and oligosaccharides are included, it still contains more than 50% of sugars, which is the largest loss of sugar and other valuables in sugar factories.

Waste molasses contains a large amount of valuable substances, but it also contains a large amount of impurities such as pigments and inorganic salts as described above, and it has a strong bitterness, pungency, astringency, and is an extremely viscous substance. Yes, it is extremely difficult to purify, and in particular, it requires a large treatment cost to remove a large amount of pigment components, which are said to be difficult to isolate microorganisms, and to dispose of pollution, so it is currently sold at a low price equivalent to industrial waste. At present, it has been mainly used as an inexpensive raw material in the fermentation industry, feed industry, etc., which can be used without requiring advanced purification treatment, but in recent years it has been a highly functional polymer film. The development of ion-exchange resins, etc. will finally cover the research and development of high-efficiency, pollution-free refining treatment methods that will enable recovery of sugars and amino acids and their edible costs even at low cost. To become It was.

Against this background, many molasses treatment methods have recently been developed and proposed. However, most of them refrain from removing pigments, or whether they are insufficient decolorizing treatments even if they are removed. Alternatively, a large amount of activated carbon or ion exchange resin regenerating agent is required, which is high in cost, or from the viewpoint of pollution prevention measures, a large amount of energy is consumed or a large amount of energy is consumed due to the concentrated incineration of a high COD-containing dilute waste liquid or the ocean dumping. There are many high-cost treatment methods that have to bear the transportation cost, low-cost production of high-quality complex sugar and edible molasses, etc. with good flavor and visual image and high-efficiency, low-cost recovery method of useful ingredients However, it can be said that many problems remain.

(Means and actions for solving problems) From the viewpoint of effective reuse of resources, in view of such circumstances, we have mainly adopted a low-cost purification method that can efficiently remove a large amount of impurities such as pigments, other inorganic salts and rubber substances. As a result of diligent research, we have devised and completed a highly decolorizing desalination purification method that has few drawbacks in terms of pollution control measures and that can efficiently remove only unnecessary impurities while efficiently recovering useful sugars and amino acids. Ivy.

That is, in the present invention, the following are the main points in which the problems of the prior art are solved and improved.

(1) Conventionally, when the membrane separation (excess) such as ultrafiltration is performed for the purpose of decolorizing and purifying sugar solutions, especially sugar solutions containing a large amount of impurities such as molasses, excess liquid containing 30% or more of sugar (concentrated Liquid) is generated as much as 20 to 30% of the processing liquid amount and removed outside the system.
Although some of the over-precision itself is extremely excellent in that it results in the generation of a large amount of unused sugar, its poor sugar recovery rate is one of the major drawbacks. By combining the sedimentation separation method and the membrane filtration method, once the liquid that has been coagulated and separated by alcohol is passed through this membrane, the polymer dye and rubbery substances in the membrane overconcentration residual liquid are removed again. Since it will be re-agglomerated with alcohol, as long as they are recycled to the alcohol coagulation settling tank of the first stage, they can be re-processed as much as possible.
We found an epoch-making method for sugar liquid membrane over-operation that can recover almost 100% of sugars while performing a severe over-treatment.

(2) When a high-pigment sugar solution such as molasses is to be completely decolorized near 100%, it has been conventionally impossible to achieve a decolorization rate of 50 to 70% due to membrane separation or sodium silicate. Therefore, a large amount of activated carbon or synthetic adsorption resin is required as a finishing decolorizing agent after that, and it requires a large amount of cost to regenerate it. Practical technology for obtaining quality edible molasses has not been developed, but in the present invention, a high color value impure sugar liquid having a color value (stunker color value = st.CV value) of 2,000 or more like molasses is used. Even if it is possible to achieve a high decolorization rate of 95% or more without loss of sugar to the outside of the system by the combined treatment of alcohol coagulation / separation decolorization and membrane filtration, it is assumed that this combination of alcohol coagulation decolorization and membrane filtration is performed. The light-colored molasses treated by Even if the finish is completely decolorized by, for example, the required amount of activated carbon is 1/5 to 1/10 or less compared with the case of decolorizing the activated carbon after the single separation and decolorization only for the ultrafiltration, and the use of the activated carbon is greatly reduced. Is possible.

(3) Conventionally, when KA electrodialysis desalting is performed after decolorizing and cleaning treatment of molasses by a usual treatment method, one of the two is due to a large amount of pigments and other organic anion substances remaining in the sugar solution. Since there is a problem that the anion exchange membrane of the above is contaminated in a short period of time, there is currently a method of preventing the contamination by frequently alternating the positive and negative electrodes, or the pH of the diluting solution or the concentrating solution is set to 2 It is necessary to take various special measures for practical use because there are various problems such as high risk of sucrose decomposition to lower the dialysis level to around 3 to prevent contamination and prevent the separate use of the concentrate. However, in the case of the sugar solution treated by the method of the present invention, since it has already been highly decolorized and highly deorganized anions, it can be applied to a KA type electrodialysis apparatus as it is or if it is subjected to a slight decolorization treatment. It can be applied easily.

(4) Since high processing efficiency can be achieved (pure sugar ratio up is 30-40 points), even two-stage decoction can be easily performed even from low-purity molasses such as waste molasses, and high quality sugar crystals can be obtained. Not only can it be collected at a high rate, but it also has good flavor and visual image as edible molasses or powdered complex sugar,
In addition, it will be possible to manufacture light-colored complex sugar products that are perfect as health food materials.

(5) Since a large amount of expensive ethyl alcohol is recirculated and used, a large amount of energy is required to separate sugar liquid and alcohol in view of the high energy consumption situation in the conventional alcohol separation and concentration technology, Although it may be a big problem in terms of cost, many promising energy-saving alcohol separation / concentration technologies (for example, pervaporation type alcohol membrane separation / concentration device and ultrasonic vibration type alcohol separation) have been made possible thanks to the progress of research on biomass alcohol utilization. Concentrators, etc.) have been developed, and in the case of the present invention, although a large amount of alcohol is recirculated and used, the concentration of recirculated alcohol is 70 to 80%, which is a medium concentration. , Improved the energy-consuming type in the conventional coagulation-sedimentation cleaning method using hydrophilic organic solvent to a drastic energy-saving type It Kosutoputsushiyu by alcohol separation energy has ceased become a problem.

(6) Concentrated incineration of a large amount of pigment liquid containing high COD, which has a low concentration as in the past, because the high-molecular-weight pigments unique to molasses, which are difficult to decompose microorganisms, and rubber substances can be aggregated and solidified without pollution. It does not require a large amount of energy to do so, nor does it require a special wastewater treatment device, and it is possible to use a large amount of highly efficient edible low-price high-pigment molasses equivalent to industrial waste such as molasses. And so on.

The configuration and features of the present invention will be described in more detail below.

First, as a first step, dilute molasses Bx to about 50-60% in advance and add about 13-15% lime milk to this to adjust the pH.
Is adjusted to 11.0 to 12.5, preferably about 12.0.

Usually, NaOH, KOH, Na ₂ Co _{3 and the} like can be considered as the alkali modifier, but the reason why it is specified as calcium hydroxide here is as follows.

That is, NaOH, KOH, etc. are usually expensive and have a high syrup-forming property, which is not desirable for the purpose of recovering sucrose.

In that respect, calcium hydroxide is inexpensive and does not have the above-mentioned drawbacks. Furthermore, since it is appropriate that the viscous sludge generated in the next step is contained and the handling operation becomes extremely easy, it is suitable as an alkali adjusting agent in this case. It can be said that calcium hydroxide is highly desirable.

The reason why the pH is adjusted to the strong alkaline region is that the higher the pH is, the higher the sugar purity can be seen, and the decolorization rate is better as the pH is higher, as can be seen from Table 1.

Next, after heating the diluted pH adjuster molasses to about 60 ° C., 70 to 95 volume (VOL)% ethyl alcohol was added to the solution.
2.0 to 12.0 times the amount of raw molasses before dilution in terms of 5 VOL% concentration, preferably about 60 times 80% ethyl alcohol is added to solid content concentration (Brix, Bx) 55 adjusted molasses, and mixed and stirred rapidly.

Molasses temperature at the time of mixing is 25 to 70 ° C, preferably 55 to 6
Within the range of 5 ° C, sugar loss is small and decolorization efficiency is good.

By the way, the concentration of molasses and the concentration of alcohol here are not particularly limited as described above, and the ratio can be changed depending on the respective concentrations. In short, molasses solid content: water: Molasses solids content 5-10 for the total amount of mixed liquid in the state of mixing pure alcohol
%, Water content 15 to 35%, and pure alcohol content 55 to 80% within a mixing range, and in the case of this mixing ratio, a higher clean decolorizing effect can be obtained with a relatively small amount of alcohol.
Furthermore, the amount of sugar loss to the sludge can be made relatively small.

In other words, the functional meaning of each mixing ratio here is that it is necessary to secure a necessary and minimum amount of water necessary to dissolve sugar as much as possible, and yet, a dye that is easily dissolved in water, It is necessary to have an alcohol content capable of simultaneously exhibiting the function of coagulating and precipitating other impurities,
If this ratio is too biased to either side, for example, if the alcohol content is too high, the removal of impurities will be improved, but on the other hand, the loss amount of sugar to the sludge will be increased, and, on the other hand, in the opposite case, the sugar content will be reduced. When the amount of water is large enough to dissolve it and the amount of alcohol decreases, the sugar loss decreases, but on the other hand, the decolorizing effect on cleanliness deteriorates. It should be understood that the mixing range is the above-mentioned mixing range.

The water contained here may come from the Brix diluted water or the alcohol diluted water, so that the molasses concentration and the alcohol concentration are relative.

As a result of this mixing, an agglomerated precipitate is immediately formed by this mixing, and this is removed and decolorized and purified by combining a settling tank, a centrifuge or the like in a one-stage or two-stage series.

However, the sugar-alcohol mixed clarified liquid obtained here has a strong alkalinity and a large amount of residual calcium content, so that it can be attached to the effect can scale during the alcohol separation and recovery operation in the next step, or from the viewpoint of preventing membrane contamination, or it can also be reduced. In order to prevent sugar decomposition, it is necessary to perform softening treatment and pH readjustment treatment to neutral range in advance. As a method for this, a method of neutralizing with a mineral acid such as Hcl or H ₂ SO ₄ may be considered, but from the viewpoint of low running cost, a method of saturing carbon dioxide gas such as flue gas. Is most preferred. By the way, under the condition of 50 ° C, carbon dioxide gas is filled in the satiety tank with alcohol escape prevention device, and if it exceeds, the residual calcium content is also about 35,000 per solid content.
Softening treatment is possible from PPM to about 7,000PPM.

In this way, it is necessary to separate, concentrate and recover the alcohol from the sugar alcohol mixture obtained by softening and pH re-adjusting treatment in this way, but this operation is as described above in the actual process. Recently, various researches on energy-saving alcohol separation / concentration technology from biomass alcohol have been carried out eagerly, and as a result, some promising technologies such as alcohol membrane separation / concentration by pervaporation method and ultrasonic vibration have been developed. It is said that these are already in the stage of practical application, such as a method for separating and concentrating high-concentration alcohol at low cost by the above-mentioned cavitation, and it can be suitably applied even in the case of this method.

For the time being, in this experiment, alcohol separation is being confirmed using a small-sized alcohol membrane separation / concentrator, but at present, these characteristics are mainly assumed from the fact that the equipment capacity is small. At the same time, the research was advanced by separating and concentrating alcohol using an evaporator.
Normally, although the total amount is significantly reduced in the alcohol membrane separation and concentration by the pervaporation method, it is not possible to completely separate the alcohol by itself.
Alcohol content remains about%.

Therefore, in order to completely separate and recover the expensive alcohol from the sugar solution, a distillation apparatus is required, but from the results of many experiments, the concentration of the residual residual concentration of alcohol is 35% or more (Bruc %, 0.35%) 50%
It has been found that it is necessary to concentrate by distillation to (0.07%) or less, preferably about 40 to 45%. (Refer to Fig. 3) The reason is that ethyl alcohol is very expensive and it is necessary to recover it as much as possible.

However, if 100% complete recovery is carried out without restriction and concentrated to a high concentration, the amount of alcohol recovered will be very small from a certain concentration stage, but only a large amount of water will be added and energy will be uneconomical. .

Therefore, in order to obtain the optimum distillation concentration, the alcohol is gradually distilled and separated from the alcohol mixed sugar solution of the second step treatment liquid, and Bx30 is added from Bx25 to Bx30 in increments of 5Bx, respectively.
35, 40, 45, 50, 60 were sampled and the residual alcohol% was measured. The result is as shown in Fig. 3. Until around Bx30, 0.6 to 0.7% of the alcohol remained, and the amount of loss was Although not negligible, it was found that from around Bx40, the residual alcohol decreased to about 0.20%, and there was a characteristic that it became an allowable concentration.

Therefore, it is considered that the concentration degree for alcohol recovery here is Bx40-45%, which is the best concentration, when comprehensively considering energy economy and excessive difficulty in the next step.

In the case of molasses, the decolorization rate of 80 to 83% is usually achieved by the series of operations up to this point, and the molasses undiluted solution color value (St.CV value) of about 2,000 to 3,500 to St.CV 250 to 350.
It is decolorized to a light reddish brown color, and in addition to the pigment component, most of the foam component, polysaccharides, gum substances, inorganic salts such as sulfate radicals, etc. are also removed, and the sugar purity and the pure sugar percentage are 22 to 2.
A significant cleaning effect can be achieved by only the alcohol treatment in the first, second and third steps, such as an increase of 5 points. (See Tables 1, 2 and 4) By the way, the ultrafiltration system has already been adopted in the pure water production and brewing departments and many other departments because of its excellent suspended solid removal performance. In the same way, it seems that this over-system should be useful and will be greatly utilized in the sugar production sector, which requires a lot of over-operation, but in reality, it has become so popular now. Why didn't I see it?

There are various possible reasons for this, but one of the biggest reasons is that when the sugar solution is passed through the ultrafiltration, the sugar purity in the fractional overconcentration exclusion solution does not decrease so much, and in the end, the exclusion concentration solution. This is probably because there is a major drawback in that the sugar loss to (1/5 to 1/6 of the total liquid volume) cannot be ignored.

One of the major characteristics of the present invention is that it can overcome and overcome the drawbacks of loose RO filtration and ultrafiltration such as ultrafiltration.

That is, in the present invention, sugar can be recovered by recycling the removed concentrated residual liquid to the pH adjusting tank in the first step.

It is theoretically unknown what kind of mechanism of action is so far, but for example, mixing the same Bx55 molasses as the series of operations up to now with 6 times the amount of 80% ethanol. Then, the clear liquid, which has been once separated by coagulation sedimentation and separated by alcohol, is subjected to high-pressure ultrafiltration of dyes and other polymers with a dynamic membrane equivalent to a molecular fraction of 10,000. When mixed with the same concentration and the same amount of alcohol as when they were allowed to stand, it is mysterious that these concentrated polymers did not aggregate and separate during the first alcohol mixing, but they passed through the ultra-high temperature. This is because it was found that those that did not permeate due to coagulation again had a mysterious property of causing alcohol coagulation and precipitation again. (See FIG. 8) As described above, in the ultrafiltration or reverse osmosis permeation system of the present invention, by combining with the process of alcohol coagulation treatment, the conventional ultrafiltration system has poor sugar recovery. There is a great feature in overcoming the drawbacks and solving them.

By the way, the color of the treatment liquid by the first, second, third, and fourth step treatment becomes a stummer color value of 70 to 150, and the color of the dull black and molasses becomes a pale reddish brown clear, and the visual image is Significantly improved, and flavor and sweetness have also been improved considerably, but a slight pungent and astringent taste remains, and edible directly or used in combination with a current efficient cation or anion exchange membrane.
Some residual dyes, anions, etc. were observed in the feed solution for electrodialysis, and it was still insufficient to adjust the pH of the salt concentrate to prevent contamination of the anion exchange membrane. Decolorization and deanion are desired.

As such an improvement method, granular activated carbon decolorization is desirable in various aspects.

From this viewpoint, a granular charcoal column was used as the next step of the decolorization step, and the Bx50 concentrated and obtained from the membrane pass step was used.
% Clear fluid was passed through a granular charcoal column. Granular charcoal 1 was used to decolorize a Stanmer color value of 150 to about 20.
It was possible to pass 6 times as much sugar solution as 6 times.

On the other hand, when the film with the same molecular fraction was subjected to ultrafiltration only and the stummer color value was 810 and decolorized with the same granular charcoal, only 1.2 per 1 granular charcoal could be passed, Alcohol treatment + ultrafiltration (UF) treatment liquid is a single UF treatment only.
It will be only 1/5, and it will be possible to significantly reduce the cost of recycling granular coal.

In addition, the granular sugar-treated decolorizing sugar solution had a pure sugar rate increased by about 5 points, the astringent taste was completely eliminated, and the flavor was remarkably improved.

The transparent molasses obtained by the above four steps has a slightly spicy taste as an edible honey, but it has an excellent sweetness and flavor and remains in a liquid state, or it can be dried as it is for cooking or pickling. Although it can be put to practical use for various purposes such as Tsukudani, it is still high in ash content, so it is better to lower the ash level from the viewpoint of sugar recrystallization recovery, confectionery, etc. Seems desirable.

By the way, as a desalting method for a liquid containing a high pigment such as molasses and a high salt content such as humic acid, a TD-type electrodialysis method which already uses a combination of a cation exchange membrane and a neutral membrane can be suitably applied. This is what the present inventors have proved in Japanese Patent Publication No. 58-53920.
% Or more, and if even if it is completely decolorized with activated carbon, etc., at a low cost, it is unavoidable to use the TD electrodialysis method, and rather as a method in such a case. It can be said that the KA electrodialysis method using a combination of a cation exchange membrane and an anion exchange membrane, which has high current efficiency and is easily desalted, is desirable. Therefore, 20 pairs of cation exchange membranes and anion exchange membranes were combined with the pale clear sugar solution (Bx40) obtained from the granular charcoal column and electrodialysis was performed for 205 minutes at a cell voltage of 0.6V. It was confirmed that the salt rate was 84% and the pure sugar rate was up to 14 points, and high efficiency and high desalination were possible.

Example 1 Waste molasses of a cane sugar factory was collected, adjusted to pH 7.0 with lime milk in advance, and diluted to 55% Burutxus to 5,000.
The sludge was removed by centrifugation at rpm for 10 minutes.

13% lime milk was added to each of the centrifugation liquids 1 as a sample, and the pH was 7.0, 8.0, 9.0, 10.0, 11.
It was adjusted to 0, 12.0 and 13.0, and this was heated to 60 ° C., and then 6% (6 times the volume) of 80% ethyl alcohol was mixed and stirred, and the resulting coagulated precipitate was passed over Toyo Paper NO. Then, the sludge was removed, and the resulting clear and sugar alcohol mixture solution was concentrated by distillation with a rotary evaporator. The results shown in Table 1 and FIG. 1 were obtained.

As shown in the table, it can be seen that the higher the adjusted pH is, the higher the pure sugar rate up is, and that the pure sugar rate up and the decolorization rate show the highest cleaning effect at a pH of 12.0.

Degradation of sucrose was observed at a pH above 12.0, and pH adjustment should be limited to 12.5.

Example 2. (Cleaning effect test according to alcohol concentration) Waste molasses was diluted in Brix 55 and centrifuged, and the separated liquid after sludge removal was diluted in Brix 50, and Bx was added to this.
800m after adjusting the pH to 12.0 by adding 14 lime milk
Prepare 7 samples of each, and heat each to 60 ℃, then separate 60%, 65%,
Adjusted to 70%, 75%, 80%, 85%, 90% concentration, and rapidly mixed and stirred atsushi 5.6 (7 times amount) of ethyl alcohol.
Then, the mixture was concentrated to about Bx51 to 60 by a rotary evaporator to completely remove alcohol, and the results were shown in Table 2.

As can be seen from the above table, when the molasses brix is kept constant and an equal amount of alcohol is mixed, the sugar purity and the decolorization rate are improved as the alcohol content concentration is increased.

However, the amount of sugar loss tends to increase when the pure alcohol content exceeds 75% with respect to the total amount of the mixed liquid, and the mixed content% is limited to about 80%.

Example 3. (Cleaning effect test by molasses temperature at the time of mixing) In the case of alcohol mixed coagulation sedimentation cleaning, waste molasses was treated with Brix 5 in order to examine the effect of temperature on the cleaning effect.
Take the centrifuge sample 6 diluted to 0 degrees and adjust it to pH 12.0 by adding 13% lime milk to it.
7 samples of 00m each are made, 20 ℃,
After heating to 30, 40, 50, 60, 70, 80 ℃, 75% ethyl alcohol 4.8 each (6 times amount)
After mixing and coagulating and precipitating, the mixture was distilled and concentrated to about 45% Brix by a rotary evaporator to remove alcohol, and then analyzed. The results are as shown in FIG.

As can be seen from the above figure, it can be said that a higher temperature is better if only the decolorization rate is considered, but from around 70 ° C the decomposition of reducing sugars becomes more vigorous and the ash content also tends to increase. It is considered to be the best around ℃.

Example 4. The concentration of molasses when mixed with alcohol is not significantly related to the cleaning effect.

Factors relevant to the cleaning effect are pH, temperature and the "solids: water: alcohol" mixing ratio.

In order to prove this, the water used to dilute Bx at each stage while keeping the molasses amount and alcohol amount at the same amount was used as the alcohol dilution water, and the cleaning ratio was kept almost constant. The test results are shown in Table 3.

As shown in the above table, as long as the mixing ratio of “solid content: water: alcohol” is roughly constant, the cleaning effect (up of pure sugar rate, color value) is almost the same regardless of diluted Bx.

Example 5. Waste molasses of a raw sugar factory was diluted in Brix 55, Sample 1 was collected in 10 poly buckets, 13% lime milk was added thereto to adjust to pH 12.0, and then 80% ethanol 6 was added.
When the mixture was mixed and stirred, an agglomerated precipitate material was immediately generated.

After leaving it for about 10 minutes, remove the sludge by the tilt method.
A clean supernatant sugar alcohol mixture was obtained.

This was divided into two, one of the three was distilled and concentrated to 54.93 by a rotary evaporator to remove alcohol, and this was used as an alcohol-clean sample. One of the three was an inner diameter of 50 m / m x length of 1,500 m / m. Transfer to a glass column with a jacket and keep it warm with 60 ° C hot water, insert a pH meter injecting electrode into the column to control, and inject carbon dioxide gas to a pH of 8.0 to inject gas. Finished and vacuum formed calcium carbonate with Toyo Paper No.2 and then Bx31.20 with a rotary evaporator.
Alcohol was completely removed by distillation until it became, and the results shown in Table 4 were obtained when subjected to analysis.

The analysis value of raw honey is also posted for comparison.

Example 6. Cane molasses was diluted to 60 Bx and centrifuged, and the separated liquid was further diluted to 25% in Brix degree, 1.4 was collected, and 14% lime milk was added thereto to adjust the pH to 12.0. After the adjustment, 92% ethyl alcohol 2.8 (2 times amount) was mixed and stirred, and the aggregated precipitate was formed after the aggregated precipitate was not removed and the carbon dioxide gas was saturated to re-adjust the pH to 8.0. The product, calcium carbonate and the like were passed through a vacuum on Toyo Paper No. 2 to remove sludge, and a clean sugar alcohol mixed liquid was obtained.

This was distilled with a rotary evaporator to obtain a concentrate having a Brix degree of 46.35%.

The concentrated liquid thus obtained was analyzed and found to be as shown in the table below.

As you can see from the above analysis results, mix alcohol,
This method, in which the aggregated precipitate is continuously filled with carbon dioxide gas in a suspended state and the pH is adjusted over, requires only one over-separation operation as compared with the methods of Examples 3 and 4. In addition, while the ash level of the treatment liquid is low and the decomposition of reducing sugar is small, the decolorization rate is slightly poor, the removal rate of magnesium is poor, and the amount of sludge is large. There is a tendency that the fluctuation of the sugar rate is large, and it seems that the method to be selected should be decided depending on whether the purpose is to recover sucrose or to purify the stock solution for fermentation.

Example 7. Alcohol mixing, coagulation, by the same treatment method as in Example 5,
Treatment liquid for waste molasses that has undergone precipitation separation and carbonic acid satiety treatment (Bx
40.50, A ・ pty56.50, St.CV292) was made about 13.5, and this was used as a sample for reverse osmosis permeation equipment (pump: Capital High Pressure Plunger R manufactured by CS Engineering)
O-31A, module: Nitto Denko reverse osmosis membrane module, negatively charged synthetic polymer composite membrane NTR-7410-S2, effective membrane area 1.25 m ² ) permeation treatment at 20 kg / cm for 360 minutes, Since a permeate of 7.5 and a concentrate of 6 (concentration of 2.25) were obtained, the analytical values of these were shown in Table 6 and the laboratory ultrafiltration device (Uw-1A manufactured by Nitto Denko: Module NTU-3000). -Table 18 shows the analytical values of the permeated liquid and the concentrated liquid when the Bx35 centrifuge liquid was ultrafiltered using P18 type, effective membrane area 0.76 m ² , tuber).

As you can see from the table on the previous page, when the combined treatment of alcohol coagulation separation cleaning and membrane filtration is performed, the color value of raw honey (St, C
V) 2,155 to St.CV77 are decolorized, and the total decolorization rate is 96.43%, which makes it possible to perform ultra-high decolorization that is hard to believe by ordinary processing methods.

This color value level is much lower than the color value level of 100 to 120 of clean juice or raw syrup of a raw sugar factory, and it is a clear syrup containing no colloid at all. Even if decolorization up to the color value level (St.CV20) is performed using activated carbon or bone charcoal, the amount used is slightly less than 1/6 to 1/10 of the amount of treated syrup, and colorless syrup is used. It's also easy to get. In addition, in order to verify whether or not the membrane over-concentrated liquid described on the previous page can be recycled and processed in the pH adjusting tank in the first step, lime milk is added to the liquid to adjust the pH to 12.0, and then 80%. 6 alcohol
Mix twice the amount, pass the re-aggregated precipitate with Toyo Paper No.2,
The concentrated liquid obtained by distilling off the alcohol and a part of the water with a rotary evaporator as in the main operation was analyzed and the results are shown in Table 8. There is no problem in terms of pure sugar rate and color value. It turns out that it can be reprocessed.

Example 8 By the same treatment method as in Example 5, alcohol mixing / aggregation / precipitation separation and carbonic acid saturating treatment liquid (Brix 36.39, purity 54.
70, Ash / 100Bx11.32, pH8.8, St.CV347) loose RO
Permeate that passed loose RO with negatively charged composite membrane (Bx3
0.51, Purity54.18, Ash / 100Bx13.63, pH8.71, St.CV14
4, 5 concentration ratio 2.85), 5 pairs of cation exchange membrane (Asahi Kasei Aciplex CK-1) and polyvinyl alcohol neutral membrane (N-4 manufactured by Taito Co., Ltd.) are combined for lab electricity with a membrane area of 57.6dm ^2. Using a dialysis device, electrodialysis (desalting rate: 78.29%) was performed for 180 minutes at a cell voltage of 1.8V.

The results are shown in Table 9 together with the analysis value of untreated molasses.

As can be seen from this table, when compared with untreated waste molasses as a standard, the pure sugar rate up is 30.86 points and the decolorization rate is 95.35.
%, Demineralization rate 80.0%, Cao / 100Bx removal rate 85.01%, Mgo / 100B
x An excellent cleaning effect with a removal rate of 96.34% was obtained, and the flavor of the treatment liquid was also excellent.

Example 9. Treated solution obtained by mixing cane sugar molasses with alcohol, coagulating, precipitating, separating, and carbonic acid saturation treatment by the same treatment method as in Example 5 (Brix 35.16, A.pty55.20, pH8.83, RS / 100Bx (%)
12.40, Ash / 100Bx (%) 11.74, St.CV336) with Nitto Denko's negatively charged loose RO membrane (NTR-7410-S2), Bx3
Bx2, where reverse osmosis was carried out at 5, 40 ° C, concentration ratio 3.37 times
7.72, A.pty54.40, pH8.94, RS / 100Bx13.12%, Ash / 100
Permeate of Bx12.12%, St.CV100 and Bx36.06, Apty57.30, p
A concentrated solution of H8.94, RS / 100Bx10.72, Ash / 100Bx9.48%, St.CV725 was obtained.

The permeated liquid obtained here was once concentrated to Bx52 for storage, 6.4 was collected from the collected, and the pH was adjusted to 6.8 with hydrochloric acid, and then the cation exchange membrane (Aciplex CK-
1) and anion exchange membrane (A-201 manufactured by Asahi Kasei Corporation) 2
Using a lab electrodialyzer with an effective membrane area of 60.48 dm ² combined in a pair, KA electrodialysis (desalination rate 78.38%) at a cell voltage of 0.5 V for 220 minutes gave the following results. It was Part of the operation record is shown in Table 10, and the analysis result is shown in Table 11.

As can be seen from Tables 10 and 11, 95% or more of the pigment components are removed even with a large amount of anionic organic substance-containing sugar solution such as pigment components such as molasses, and all polymer colloids are removed with a high precision called loose RO filtration. If electrodialysis is performed after that, dialysis can be performed with almost no decrease in the pH of the sugar solution to be treated.
It is also possible to prevent contamination of the anion exchange membrane.

(Note) Sugar cane molasses contains a large amount of reducing sugars and amino acids,
When electrodialyzing in an alkaline region having a pH of 8.0 or more, the carbonic acid saturate liquid pH was 8.6 in the present example because it tends to be colored, but the pH was further adjusted to pH 6. After readjusting to 8, ED treatment was performed.

Example 10. Sugar cane molasses was diluted to Bx55, heated at 60 ° C, and then heated to 80%.
Six times the amount of alcohol was mixed, coagulated, sedimented, and cleaned, and after carbon dioxide gas satiety, the concentrated solution separated with alcohol was made Bx40 and
Self-exclusion dynacellum membrane module (D)
C0305, membrane area 0.16m ² × 2) and high pressure ultrafiltration (2
(0 kg / cm) was used as the permeated liquid, and was manufactured by Toyo Calgon Co., Ltd. C
Under conditions of SV = 1,60 ° C. using AL granular activated carbon, Bx43.04 per activated carbon was passed through 8 times per resin for decolorization rate of 68.5%, and decolorization solution 6 was collected and cation exchange membrane ( Asahi Kasei's Aciplex CK-1) and anion exchange membrane (Asahi Kasei's A-201) 21 pairs of membrane area 60.
Using a 48 dm ² laboratory electrodialyzer, cell voltage 0.6 V, 2
After electrodialysis for 05 minutes, the demineralization rate was 75.59 (the desalination rate was 84.
It was confirmed that the current efficiency was 95.3% and the pure sugar rate uppoint was 14.76, indicating high efficiency and high desalination. The results are shown in Table 12.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between the adjusted pH, the decolorization rate and the up point of the pure sugar rate, and FIG. 2 is a diagram showing the influence of the temperature on the cleaning effect when alcohol coagulation / precipitation is performed. The figure is a diagram showing the relationship between the evaporation concentration (Brix) and the residual alcohol%.

Claims (6)

[Claims] 1. Addition of water and calcium hydroxide to molasses
Solid content concentration (Brix) of 0 to 80% by weight and pH of 11.0
Adjust the pH to within the range of ~ 12.5, and further adjust this to 25 ~ 70 ℃
After adjusting the temperature within the range of, the molasses is mixed with the adjusted molasses in an amount equivalent to 2.0 to 12.0 times the molasses volume before dilution in a 95% by volume concentration of ethyl alcohol equivalent amount, and the solid content of molasses is 5 to 10. A first step of preparing a mixture of 15% by weight, a water content of 15 to 35% by weight, and a pure alcohol content of 55 to 80% by weight, and removing the coagulation-precipitated suspended matter produced to perform decolorization cleaning, and a treatment liquid for this first step. Satisfied with carbon dioxide
A second step in which the calcium carbonate formed by re-adjusting to pH 7.0 to 9.0 is separated and CaO is reduced to 7,000 ppm or less,
Furthermore, the treatment liquid in the second step can be used as it is, or further using a mineral acid.
The process of concentrating the sugar liquid concentration to 35 to 50% of Brix by separating and concentrating the alcohol content and a part of the water after adjusting the pH to 7.0 to 5.0 is the third process, and then the third process treatment concentration. Negatively charged synthetic polymer reverse osmosis composite membrane that shows permeability in the loose RO region, or molecular fraction about 1
10k using a dynamic membrane showing a permeability equivalent to 0,000
A decolorizing and cleaning method for molasses, which comprises a fourth step of obtaining a highly decolorized cleaning liquid by passing a high-pressure membrane of g / cm or more. 2. Water and calcium hydroxide are added to molasses to add 3
Solid content concentration (Brix) of 0 to 80% by weight and pH of 11.0
Adjust the pH to within the range of ~ 12.5, and further adjust this to 25 ~ 70 ℃
After adjusting the temperature within the range of, the molasses is mixed with the adjusted molasses in an amount equivalent to 2.0 to 12.0 times the molasses volume before dilution in a 95% by volume concentration of ethyl alcohol equivalent amount, and the solid content of molasses is 5 to 10. A first step of preparing a mixture of 15% by weight, a water content of 15 to 35% by weight, and a pure alcohol content of 55 to 80% by weight, and removing the aggregated and precipitated suspended matter produced by decolorization cleaning, and a treatment liquid of this first step Satisfied with carbon dioxide
The second step of re-adjusting the pH to 7.0 to 9.0 to separate the formed calcium carbonate and reducing it to 7,000 ppm or less as CaO, and the second step treatment liquid as it is or further using mineral acid to adjust the pH.
Readjusted to 7.0-5.0, and then the alcohol content and some of the water content was once adjusted to 25-5% by volume of residual alcohol content in the sugar solution.
The third step of separating and concentrating and reducing the volume to such an extent, and this alcohol-containing third step treatment liquid is a negatively charged synthetic polymer reverse osmosis composite membrane showing permeability in the loose RO region, or a molecular fraction of 20,000 or less. The fourth step of obtaining a highly decolorized permeate through the ultrafiltration membrane of, and further using a multistage rectification column,
A method for decolorizing and cleaning molasses, which comprises a fifth step of recovering a high concentration of residual alcohol. 3. The alcohol separating and recovering device of the fifth step is a multi-effect can, wherein the concentration of the sugar solution is also concentrated so that the concentration of the sugar solution is 35 to 55% while collecting the residual alcohol. A method for decolorizing and cleaning molasses according to item 2. 4. Sufficient carbon dioxide gas in the second step without sacrificing after mixing alcohol in the first step,
The method for decolorizing and cleaning molasses according to claim 1, claim 2 or claim 3, wherein the aggregated precipitate, calcium carbonate and the like produced after the pH is readjusted to 7.0 to 9.0. 5. A method for preventing loss of sugars outside the system by returning the fractionated and over-concentrated residual liquid of high-pressure membrane filtration in the fourth step to the first step and carrying out alcohol mixing reaggregation separation treatment. A decolorizing and cleaning method for molasses according to any one of 1 to 4. 6. A decolorized and purified concentrated molasses liquid as it is, or after it is further brought into contact with activated carbon, bone charcoal, or a synthetic adsorption resin to finish decolorization, and a cation exchange membrane and a neutral membrane are used in combination. The molasses according to any one of claims 1 to 5, wherein desalting treatment is performed by an N-type electrodialysis device or a KA-type electrodialysis device that uses a combination of a cation exchange membrane and an anion exchange membrane. Highly decolorized desalination purification method.