KR820000813B1 - Method for chromaticgraphic separation of fructose/dextrosf solutione - Google Patents

Abstract

Tight packing of an adsorbent in a sepn. column with a chamber >=1.83 m wide comprises firstly mixing the adsorbent with an excess of a conc. reagent which causes the adsorbent to contract reversibly in its presence. The adsorbent is then packed in the contracted state, into the chamber of the sepn. column and effectively enclosed. The excess reagent is then removed to cause the adsorbent to swell so that the chamber becomes fully and uniformly packed with the adsorbent particles. The process is esp. useful for preparing technical scale ion exchange units contg. e.g. Ca salts of cross linked ring-sulphonated polystyrene esin adsorbents used in the sepn. of mixed fructose- and dextrose sugar solns.

Description

Chromatograph Separation of Fructose / Glucose

1 is a plan view of a large capacity commercial fructose / glucose separator system,

2 is a schematic side view showing a detailed structure of a separation column used in the separation device system of FIG.

FIG. 3 is a partially omitted schematic view, generally taking line 3-3 of FIG. 2, showing a ring structure reinforcing the top and bottom walls of the separation column.

4 is an enlarged cross-sectional view showing a detailed structure of the resin holding device and the flow distribution device, generally taking the area A of FIG.

5 shows typical concentration profiles of the three column system effluent flows.

The present invention relates to a method for separating fructose / glucose sugar solution by chromatographic method using a large diameter bed of ion exchange resin of strong cationic salt.

The cation exchange resin is densely and uniformly filled in the separation column by a resin loading method which involves washing the resin with a salt selected from salts of calcium, barium, strontium and silver.

The shrinked resin is then put into the column to completely fill the column. After sealing the column, the resin is expanded in a defined separation column chamber by washing off excess salt.

By uniformly and densely filling the resin into the separation column chamber, it eliminates the need for a mechanical baffle that has previously been required to ensure a regular and uniform flow through the shear area of the separation columns.

Since undesired channeling or irregular flow in densely packed resin beds is practically excluded from the column filling method of the present invention, a straight separation column without a baffle is provided by the column filling method of the present invention. It becomes possible.

Fructose and glucose-containing liquid feed streams and another stream, elute Nater, are alternately fed through a series of separate columns, in periodic instantaneous phases. . The liquid streams further divide the fructose-rich and glucose-rich streams, further increasing the separation of the output stream, which is redistributed between successive series of columns.

The present invention relates to a process for separating a mixed fluid rapid stream into a plurality of fluids.

The use of strong cation exchange resins to separate fructose and glucose has already been announced. In the past, these mixtures were characteristic by-products of sugar production from sugar cane or sugar beet.

Invert sugar, in which approximately 50% of fructose contains 50% of glucose, has been separated into a portion rich in fructose and a portion rich in glucose by liquid chromatography.

This process is sometimes called molecular exclusion. Recently, a high fructose corn syrup sweetener containing 40-45% fructose, 40-50% glucose, and about 3-8% high molecular polysaccharides by the isomeridation process. Commercialization is possible, but these sweeteners are less sweet than sugar.

Sweeteners containing 55-65% fructose have almost the same sweetness as sugar and can be used directly in place of sugar in food production.

Since the cost of increasing fructose to levels above about 45% by enzymatic treatment greatly accelerates the use of the commercial methods of the present invention, efforts have been made to further increase the fructose content in these sugar mixtures by liquid chromatography. .

A method for separating fructose and glucose-containing sugar solutions by chromatographic method has been proposed, in which sulfonated polystyrene resins or other adsorbents are cross-linked with a mixture of fructose and glucose and substituted with hydrogen atoms in the nucleus. It has been used as a means of increasing the fructose content of fructose / glucose containing syrup by passing through an adsorptive resin bed containing a cationic salt of.

When using the aforementioned resins, fructose has a greater affinity for the resin than glucose has and therefore fructose remains in the resin bed while glucose passes through the effluent stream. The sugar and effluent streams are alternately fed into the resin bed, and the effluent contains a glucose-rich portion followed by a fructose-rich portion that is collected separately. Many efforts have been made to improve the efficiency of the separation process, which can be scaled up to large commercial systems.

Flow dynamics through the large separation columns must be carefully adjusted to achieve proper separation.

Several processes and systems have been proposed for the most efficient separation of fructose from glucose by molecular removal.

U.S. Patent No. 2,911,362 describes extensively the concept of using a strong cation exchange resin to separate two or more water soluble organics, including glucose, acetone, sucrose, glycerin and triethylene glycol. This reference generally describes the separation of aldehydes and ketones. Among the resins described in this patent include granular cation exchange resins, which are the general form but hydrogen type used herein. This resin is one of the sulfonated copolymers of styrene, ethylvinylbenzene, and divinylbenzene.

The method of preparing streptomycin with excellent activity by absorbing it into aluminum by chromatographic method is described by Williams et al. Under the title of “Chromatography”, Chemical Engineering, Nov. 1948 Vol. 55: 133-8.

In addition to aluminum, other adsorbents include activated carbon, silica gel, floridine and zeolite.

This reference describes absorption columns up to 3 feet in diameter and up to 12 feet in height.

A method for separating D-glucose and D-fructose from invert sugar or sucrose is described in US Pat. No. 2,813,810. D-glucose is separated from invert sugar or a mixture of the same amount of D-glucose or D-sucrose, which is separated by stirring with a ketone containing a small amount of water in the presence of a cation exchange resin.

Preferred cation exchange resins are sulfonated phenol formaldehyde exchange resins, sulfonated polystyrene ion exchange resins (hydrogen ion form) substituted with hydrogen atoms of the nucleus, and sulfonated types such as sulfonated coal.

US Pat. Nos. 3,044,904, 3,044,905, and 3,044,906 use chromatographs to separate glucose and pentose sugars (fructoses) using various resin salts of sulfonated sorene cation exchange resins substituted with hydrogen atoms of the nucleus. Is announced. Lactose (fructose) in the mixed fructose / glucose feed stream is selectively absorbed by the resin and most of the glucose remains dissolved in the liquid around the cation exchange resin. Glucose is then drawn out of the column by elution water, which acts to separate the fructose from the glucose.

The typical separation column described in US Pat. No. 3,044,904 is approximately 3,75 inches in diameter and filled to 38 inches deep. The calcium salt form of this resin was used in this patent.

It has been found that the flow rate is satisfactory at 0.1 to 0.4 gallons per minute per square foot of cross section, and the temperature is preferably in the range of 50-70 degrees Celsius.

US Patent No. 3,416,961 describes a recycling system for chromatographic separation processes such as described in US Pat. No. 3,044,904.

US Pat. No. 3,817,787 uses the same cation exchange resin stream and describes the preferred column length for a more efficient separation process.

The dynamic packing method for charging ion exchange resins in chromatographic columns is described in Journal of Chromatography, Vol. 42, (1969) pp. 263-65. It should be noted, however, that the size of the filled resin particles ranged from 5-10 microns and the diameter of the column was only 0.62 cm.

The filling methods described include filling dust resin into a cartridge or chamber and then pushing the resin in the cartridge or chamber into a column to change its position. There is no mention of expanding the resin here.

It has been observed that the calcium salt form of sulfonated polystyrene cation exchange resins substituted with hydrogen atoms of the nucleus occupies less volume in the presence of strong salt solutions, but no useful method of applying this phenomenon has been found in the prior art. An example is U.S. Patent No. 3,928,193.

Expansion and contraction of resin beds is described in US Pat. No. 3,928,193 as "annoying." This patent describes problems caused by uneven flow of rapid flow and effluent, and an open top resin bed that alternately pumps rapid flow and effluent in order to ensure a uniform flow of liquid through the column. top-resin bed).

The U.S. Patent No. 3,928,193 refers to two other U.S. Patents: 3,250,058 and 3,539,505. See also U.S. Patent No. 3,374,606, published on the same original patent application on which U.S. Patent 3,250,058 is based.

All three of these patents focus on the distribution structure to enhance the separation ability of resin bed columns. Mechanical flow distributor devices to redistribute flow patterns to eliminate the effects of drift and turbulence in the resin bed and to improve the resolving power of large diameter columns. ) Are inserted at regular intervals.

U. S. Patent No. 3,250, 058 includes disc-shaped or donut-shaped baffles alternately arranged at intervals not greater than the diameter of the column in the overall length of the resin bed. The relatively “diameter” glass tube columns described in the patent had an inner diameter of about 49 mm (about 0.2 inches) and the columns were about 4 feet in length. See column 3 and column 5 of US Pat. No. 3,250,058.

Related patent 3,374,606 describes the use of sieve plates arranged at regular intervals in a chromatographic column. The diameter of the “large” column described here was 4 inches (6.16 cm).

The detailed description seems to be directed to gas chromatograph columns using liquid carriers such as helium, nitrogen, argon, hydrogen methane, water vapor and the like (see US Pat. No. 3,374,606, line 61-63, column (3)).

U. S. Patent 3,539, 505 pays particular attention to “large” columns in order to separate the liquid flow by the chromatographic method. Fluid mixing devices are arranged at regular intervals throughout the column length to prevent “distortion travel” of the liquid fronts of different concentrations in the column length when rapid and eluent flow alternately through the column. This reference pointed out that “distortion driving” cannot be avoided even if the process is carried out very carefully.

The largest of the so-called “diameter” columns described in US Pat. No. 3,539,505 are 1.2 meters in diameter (about 3.96 feet) and 15 meters (48.2 feet) in length. See.)

Timmins et al., “Large-Scale Chromatography: New Seperation Tool”, Chemical Engineering, Vol. 76, pp. 170-178, May 1969, published a gas chromatographic column (p. 177) with a diameter of 14 feet, which includes a "radial mixing device for suppressing non-uniformity" (p. 178) and possibly US patents. It seems to be in the form described in heading 3,250,058.

This reference also describes a liquid chromatographic column that includes a radial mixing device, wherein the largest of the liquid separation columns described herein is only about 4 feet in diameter, which is described in US Pat. Even with the use of radial mixing devices as described in US Pat. No. 3,250,058, it is very difficult to suppress drift and turbulence in the liquid system.

There are several recent patents aimed at modifying the process described in US Pat. No. 3,044,904. For example, U.S. Patent No. 3,488,031 converts sucrose and then contacts an aqueous solution of sucrose or an aqueous solution of sucrose containing invert sugar with an ion exchanger filled with calcium ions containing 1-30% free acid groups. He explains how to recover glucose from fructose.

U. S. Patent No. 3,416, 961 describes a method of the type disclosed in U. S. Patent No. 3,044, 904, wherein the outflow is divided into at least six parts and at least two of these six parts are recycled through a separation column.

The columns used in US Pat. No. 3,483,031 were 15 cm in diameter (about 5.9 inches). It should be noted that the water side and swelling of the resin are the disadvantages that can cause the glass column to explode and are described in column 5, lines 11-14. In order to avoid the undesirable consequences caused by this resin's properties, the patent applicants used six glass tubes, each 2 meters in length, instead of having a total resin bed depth of about 9 meters (about 32.7 feet). A resin bed only 1.5 m deep and only 15 cm (about 5.9 inches) in diameter was held in each glass tube.

U. S. Patent No. 3,416, 916 also describes a resin bed with more space (see column 7, lines 48-50).

The process method of the present invention provides a method for actually enhancing the efficacy of separating the mixed sugar solution by chromatographic method using a large diameter separation column containing dense and uniformly packed particulate adsorbent. The method of filling the adsorbent in the separation column advantageously takes advantage of the fact that some adsorbents decrease in volume when exposed to concentrated salt solution and again increase in volume when the adsorbent is washed to remove excess unbound salt. will be.

After the separation column is filled with a contracted adsorbent by capacity, the column is sealed and the adsorbents washed and they expand and compactly fill the column chamber.

The present invention provides a method for densely packing an adsorbent in a separation column having a chamber, wherein the process consists of the following steps:

(A) adsorbent is mixed with excess concentrated reagent, which causes the adsorbent to shrink in its presence, and the adsorbent has the ability to expand when the excess concentrated reagent is removed; Treating at a reduced volume within the column;

(B) effectively confining the adsorbent in the chamber of the separation column;

(C) removing excess concentrated reagent from the defined adsorbent so that the adsorbent can expand completely and uniformly throughout the separation column chamber.

The present invention further provides a process for separating mixed fluid feed streams containing various substances into several fluids each containing a higher concentration of one of the preceding materials than the mixed fluid feed stream. The effluent stream and the elution fluid stream are alternately passed through a separation column with a chamber to produce an effluent stream (where the chamber contains an adsorbent that is selectively affinity for one of the electrical materials), respectively. The effluent streams of are ones in which the concentration of one of the electrical substances is high, and then each of the continuous portions of the effluent stream which has at least one of the electrical substances higher than the other is collected. It is densely packed into the separation column by means of a process method in which:

(A) adsorbent is mixed with excess concentrated reagent (concentrated reagent causes the adsorbent to shrink, in the presence of the reagent, and removing the excess concentrated reagent can cause the adsorbent to expand) and shrink the adsorbent in the separation column Treating at the prepared volume state;

(B) effectively confining the adsorbent in the chamber of the separation column;

(C) allowing the adsorbent to expand by removing excess concentrated reagent from the confined adsorbent to ensure complete and uniform filling throughout the separation column chamber, to eliminate drift and turbulence, and to maintain the column chamber as it flows through the column. This step is to promote uniformity of flow velocity on the cross section.

The apparatus used in the present invention is used for large-scale separation of liquid mixtures of passing materials, which consists of several:

A) at least one separating column comprising a side wall and generally horizontal top and bottom walls defining the chamber, the chamber being 6-30 feet in length in the horizontal direction; Vertical length is at least 4 feet and does not have any internal flow distribution structure).

B) an adsorbent material which is densely packed in the chamber and which has a substantially reduced void volume than normal void volume to exert positive pressure on the wall of the chamber.

C) a fluid flow distribution device comprising devices for confining adsorbents disposed on the upper and bottom walls of the chamber as described above, wherein the device distributes the fluid flow evenly with respect to the cross-sectional horizontal plane of the adsorbent, Ability to collect effluent streams evenly.)

D) fluid collection devices capable of separately collecting portions of the liquid effluent stream flowing from the aforementioned fluid flow distribution device as the fluid mixtures pass through the device.

Adsorbents are preferably sulfonated polystyrene cation resins that are crosslinked and substituted with hydrogen atoms in the nucleus, preferably crosslinked with 3-8% divinylbenzene. The cation bound to the resin is preferably alkali metal, alkaline earth metal or silver, and more preferably calcium, barium, strontium, or silver, most preferably calcium. The concentrated reagent used to shrink the adsorbent is preferably a concentrated solution of a cationic salt bound to the resin.

The filling system described herein is particularly applicable to calcium salts of sulfonated polystyrene resins that are crosslinked and substituted with hydrogen atoms of the nucleus. These resins are particularly suitable for the separation of fructose and glucose mixed sugar solutions, such as Amberlite XE 200 (Rohm & Hass, Inc.), Dowex 50 WX ₄ (Dow Chemical, Inc.) and Zeokart 225 (Permutit, Inc.). It is sold under various brand names. These resins are usually sold in the form of hydrogen or sodium ions and have a normal pore volume of about 30%.

Treatment with strong calcium chloride solution causes the resin to shrink to less than 90% of its original volume. The separation column is then filled with shrinked resin and the resin is confined therein.

The defined resin is washed with water to remove unbound salts. The resin expands to generate a positive swelling pressure inside the separation column. This swelling pressure ensures that the resin is uniformly and densely packed into the column and that the liquid bed is densely packed and the turbulence is prevented by the densely packed resin bed when the liquid passes through the column.

The resin filling method of the present invention enables the use of a large diameter adsorbent bed without requiring an internal control plate or flow distribution structure. The present specification describes a separation column resin bed up to 14 feet in diameter and up to 7 feet in height, in which a large diameter resin bed can be used without requiring an internal flow distribution structure, thereby substantially It is noted that the total outflow volume from the device can be increased.

In the apparatus described, several cylindrical columns of 14 feet in diameter and 7 feet in height are arranged in series. Each column contains a dense and uniformly packed particulate adsorbent and also flow means for passing the continuous columns to deliver rapid, eluent and possible recycle streams in a predetermined arrangement. Is have.

The volume and total time for a particular feed stream to flow into the column is adjustable to the desired output stream and the input stream.

The outflow can be controlled by the number of refraction sensing device or the optical rotation sensing device and the timing device or a combination thereof. The volume of the influent feed stream can vary from 0.3 to 1.0 of the volume of resin bed per cycle of feed stream.

For the systems described herein, the volume of effluent required is about 0.6 of the resin bed volume when the influent feed stream is about 0.5 resin bed volume.

By using an influent stream containing 42% fructose, 50% glucose, and 8% polysaccharide, but containing about 50% dry solids, the outflow can be controlled, resulting in a 30% fructose concentration. To 99% or more can be obtained. At present, the planned flow rate through this system is about 0.4-0.7 gallons per minute per square foot, and the system works best when operating within a temperature range of 120 to 160 degrees Fahrenheit.

Large diameter separation columns used in the present invention provide an economical method for separating mixed sugar solutions containing fructose, glucose and other polysaccharides by chromatograph method. These fructose-rich sugars are derived from corn starch, which has a sufficient supply. These fructose-rich corn sweeteners provide the same sweetening effect as low-calorie sugar at low cost.

Referring specifically to the separator shown in FIG. 1, (1-9) in the separation columns 1-1 are initially loaded with Amberlite XE-200 resin supplied from the resin loading tank 2. The resin is first mixed with 20-25% by weight calcium chloride solution to make a mixture and shrunk to the desired void volume. The calcium chloride solution is supplied from the elution tank 3 to the resin loading tank through the washing water pipe 4a. Each separation column from (1-1) to (1-9) is completely filled with the shrunk resin to seal the column although there is a wash water pipe (4). Demineralized water is then fed into each column containing the shrinked resin to wash away excess calcium ions, thereby allowing the resin to expand. Since the columns are sealed, the resin can only expand within itself, so the void volume of the resin is reduced and the resin particles are densely packed. The expansion of the resin also causes a positive pressure on the separation column, which ranges from 3 psig to 17 psig depending on the degree of contraction and subsequent expansion and the degree of shrinkage and expansion is directly proportional to the extent of the calcium chloride solution. The value measured near the base of the column should be corrected because of the additional pressure of the column, but the swelling pressure of the resin is independent of the column height.

Typical swelling pressure applied to the walls of the column is about 3-10 psig when using 20% calcium chloride solution. Each separation column from (1-1) to (1-9) is generally constructed as shown in FIGS. 2 to 4 of the accompanying drawings.

The columns are cylindrical and have a cylindrical side wall 5, an upper wall 6, and a bottom wall 7. The upper wall 6 is reinforced with a hemispherical header 8 and the bottom wall 7 is reinforced with a similar hemispherical header 9. The columns (1-1) to (1-9) are all about 7 feet high and about 14 feet in diameter. Because of the resin filling method used, no internal throttle in the columns is required. The headers 8 and 9 include a flow distribution conduit 10 communicating with the inlet pipe 11 and the discharge pipe 12 shown in FIG. The headers 8 and 9 also have a number of annular rings 13 which serve to support the top wall 6 and the bottom wall 7 in a substantially horizontal plane which does not actually move. In order to maintain adequate separation efficacy, it is important to make the flow of liquid through the separation columns as uniform as possible over the entire width of the resin bed. The concentration of the effluent exiting the lowest horizontal plane in the resin bed of the third separation color should be as uniform as possible to obtain the most efficient fructose / glucose separation.

A generally closed access opening 14 can be used as a means for loading the resin into the column. A generally closed access opening 15 of the same shape is located near the base of the side wall 5, which can be used as a means for withdrawing resin from the column and also as an access means for cleaning the interior of the column.

The top wall 6 and the bottom wall 7 each include an inner stainless steel retaining screen 16 which serves to confine the resin in the column. Currently, NEVA-CLOG screens manufactured by Multi Metal Wire Cloth, Inc., Tappan, NY, are used as resin retaining screens. This is described in US Pat. No. 3,052,360.

The lattice structure 17 of stainless stil is disposed just outside the holding screen 16, and the holding screen 16 and the resin 18 are kept at regular intervals from each of the end walls 6 and 7 of the column. Doing. Lattice 17 provides a dispensing flow arrangement for liquid feed and elution water entering and exiting the column through conduit 10, which is connected to each of the end walls 6 and 7 of the column. It is in communication with several holes 19. Currently, the grating structure 17 is comprised of a 16 gauge wide stainless stil with a diameter of 0.095 inches. The special lattice structure 17 used in the recent years is sold under the trade name POR-O = SEPTA and is also manufactured and sold by Multi-Metal Wire Cloth, Inc. in Tappan, NY.

4 illustrates in detail the connection of the conduit 10 through the end wall 7.

The conduits 10 are arranged at regular intervals across the end walls 6 and 7 to allow the conduits 10 from the lattice structure 17 adjacent to the resin retaining screen 16 or into the lattice structure 17. Through 6) and (7) the distribution of the liquid flow is made uniform.

The direction of the liquid flow may be reversed to backwash the system if deemed necessary.

The resin (18) currently in the column is Amberlite XE-200, available from Rohm & Hass Corporation, Philadelphia, PA. The resin is taken in the form of sodium salt and converted to calcium salt form by the column filling method described above.

Amberlite Xe-200 resins are described as sulfonated polystyrene resins that are strongly cationic, crosslinked and substituted with hydrogen atoms in the nucleus. The resin is crosslinked with about 4-6% divinylbenzene by weight to make it more stable. The particle size of the resin is in the range of 200-500 microns (30-50 mesh).

The resin can separate fructose from feeds containing fructose, glucose, and other polysaccharides, where the feeds are driven through the column at a controlled flow rate with a continuous wave of a predetermined volume, each wave of the effluent This is possible if it leads to a wave. Depending on the difference in affinity between the resin and the individual sugars, the sugars in turn escape from the column. Polysaccharides come first, followed by glucose, followed by fructose. Continuous waves of the effluent release the fructose into the effluent, resulting in a wave of fructose-rich effluent followed by an abundant wave of glucose and polysaccharides from the previously treated effluent. It has become clear that the separation action is directly related to the length of the resin bed and the amount of effluent used to remove fructose from the bed. Fructose-rich effluent is collected by periodically switching the effluent stream from the last continuous separation column to the product tank when the fructose content is 27-32% or more.

These various flows are pumped out through the device by the pump 20 in a time-controlled order. The flow of rapid and effluent water passing through each column is regulated by valves 21 and 22, which are actuated by a dual control unit 23 so that when valve 22 is opened, valve 21 is closed and vice versa. When 21 is opened, the valve 22 is closed to alternate the flow of rapid flow and elution water in accordance with a signal received from the control device 23.

In the apparatus used in the present invention, (1-3) in the separation column (1-1) are operated continuously in a row. (1-6) in the separation column (1-4) is operated in the next row and (1-9) in the separation column (1-7) is operated as the third column of the column.

Rows of three adjacent columns usually work together simultaneously and work as a unit. Additional columns can be used to increase the overall output of the device, which increases in proportion to the number of columns added. The columns operate at the same time period, or while the other rows of columns accept rapid flow, the other columns operate alternately to accept eluent.

The separation column at the far end of the column comprises an outlet tube 24 having outlets 25 and 26. The direction of flow to outlets 25 and 26 is controlled by valves 27 and 28, respectively, which are valved when valve 27 is closed by a double bottom device 92, similar to controller 23. 28 is adjusted in an open manner. The outlet 25 is adjusted to open when fructose-rich eluate leaves the column 1-3 through the tube 24.

The fructose content of the effluent stream is inspected using a refractometer 30 and a photometer 31, with the correct adjustment of the valves 27 and 28 so that the desired product is passed through the tube 24 to the product tank 32. To be sent to. If the product is not delivered to outlet 25, valve 28 is opened and what is coming out of column 24 of the column is sent to return flow tank 33. The material in the regression tank 33 is recycled through the device to remove the remaining fructose, or convert the polysaccharide to glucose by an isomerization method or an enzymatic conversion device using glucoamylase and other processes. Regression flow can also be sold as a low-end product, depending on possible economic benefits.

The product in the product tank 32 is usually lower in concentration than commercially required and needs to be evaporated to reduce the moisture content.

A typical high fructose product after evaporation contains about 74-78% of dry solids and contains about 55% fructose, 42% glucose and 3% polysaccharides by weight.

The heaters 34 and 35 are placed on the eluent tank 3 and the raw sugar feed tank 37, respectively, to maintain the temperature of the effluent and the feed stream in the range of 140 to 160 degrees Fahrenheit. Operation at lower temperatures results in microbial contamination of the resin bed, while temperatures above 160 degrees Fahrenheit present a risk of discoloration of the product. The presently preferred product is colorless.

While the device is in operation, as the fluid flows through the bed filled in the separation column (1-1) (1-9), the pressure of the liquid rises and falls in a periodic pattern. During normal separation operations, the compressibility of the resin bed, the column height, and the flow rate are actually constant. The main variable is the cyclic liquid pressure change caused by the change in viscosity as the concentration of feed crude sugar varies from the minimum water to the highest crude sugar concentration.

Amberlite XE-200 resin can separate glucose from fructose by molecular exclusion.

Fructose is loosely held in the form known as the calcium-fructose complex by the resin bed. Fructose remains tightly bound to the resin until the effluent stream apparently weakens the drag of fructose to the resin and elutes the fructose from the resin in a periodic manner as indicated in FIG. It is possible to increase the fructose concentration in the elution stream by increasing the amount of effluent or by separating the glucose and polysaccharides from the fructose by recycling the fructose-rich stream. It is possible to obtain practically pure fructose by using various recirculation units and by adding additional effluents, but economic factors must also be taken into account.

The time and power it takes to recycle the streams, the cost of power to evaporate the more diluted product, and the commercial demand, all of these factors must be considered in determining the concentration level of fructose to be produced by the device.

At present, all of the aforementioned factors produce products in which the concentration of fructose is in the range of 55-65% by weight fructose. The glucose content of these products is in the range of about 40-50% by weight and the content of polysaccharides is kept below about 8% by weight.

5 shows the concentration profile of the above-mentioned device when the incoming feed stream is 42% desalted fructose, 50% desalted glucose, 8% desalted polysaccharide and dry solids of about 50% coon syrup. . Rapid feed sugars can be obtained from the enzymatic isomerization method. The desalted effluent is alternately sent to the separation column apparatus via conduit 4 alternately with the feedstock sugar fed through conduit 38.

Using the preceding 42% fructose feed stream in the separator described above, the cycle required to pass (1-3) in column (1-1) takes about 330 minutes at a flow rate of 0.5 gallons per minute per square foot. During this typical 330 minute cycle the concentration of the effluent increases from 1% to 48% by dry solid weight ratio within about 150 minutes and then decreases by 1% dry solid weight ratio by 180 minutes.

During the same time, the fructose content of the effluent stream increases from 0% to 90% of fructose within about 250 minutes and then rapidly decreases to about 0% concentration for 80 minutes. If a product with a fructose content of 55% is desired, the effluent is sent to the product tank 32 when the fructose content is in the range of 28-32% or more and a regression flow tank (if the content of fructose is lower than 28-32%) 33).

Both inflow and effluents should be maintained within a flow rate of about 0.4-2.0 gallons per minute per square foot.

Increasing the flow rate results in a greater pressure drop across the column and results in somewhat inefficient separation, but increases the outflow volume. The most appropriate flow rate should be determined based on measurements taken taking into account the overall process costs for a particular device.

If you want to make a product containing 90% fructose using the above-mentioned separation device, it is recommended to use the following process.

As described above, feed streams containing 50% dry solids, including 42% fructose, 50% glucose, and 8% polysaccharides, are fed to the column for a period of time, with 0.2- percent of resin volume per cycle. 0.3 volume is dispatched.

The flow rate is 0.4-0.7 gallons (0.4-0.7 gal / min / ft ² ) per square foot per minute.

If the effluent stream from the device contains 60-75% fructose and 20-30% or more of the dry solid component, the effluent stream is a recycle stream that is returned through the columns. After the aforementioned recycle stream is fed to the column, the eluent with a pH of 4-5 is added immediately. The total volume of effluent should be in the range of 0.2-0.7 of the resin volume per cycle if the flow rate is 0.4-0.7 gallons / minute / square feet. If the recycle stream effluent from the unit contains 80-87% fructose and at least 5% dry solids, the effluent is sent to a product tank and collected into the product.

The total fructose concentration of this product is about 90% or higher. The average dry solid content of the products is about 16% and is further purified by filtration, evaporation, desalting, etc. to obtain 79.5-80.5% dry solids, 90-92.5% fructose, about 5-7% glucose, about 1-3% Produce products containing polysaccharides.

The foregoing descriptions illustrate the apparatus used in the present invention and there is considerable flexibility in the method of the present invention. Fructose containing raw sugars ranging from the smallest amount of fructose to virtually pure fructose can be economically separated from mixed sugars containing fructose, glucose and other polysaccharides. From the same sugar mixture, products can be obtained ranging from small amounts of glucose to substantially pure pure glucose. As the fructose concentration increases from 55% to 95%, the cost of separation also increases, but with the above device, 95% of fructose syrup can be made three times more than the cost of making 55% fructose syrup. It is estimated to be.

These sweet products are especially needed in pharmaceutical preparations and as special dietary ingredients.

Recirculation of effluent and other effluents further reduces the production rate.

The resin filling apparatus used in the present invention is very useful because it can use a large-capacity column of more than 12-14 feet in diameter without the additional cost of the internal regulator. The liquid dispensing device provided between the columns makes the flow through the entire column system uniform and also allows for more effective product separation. The amount introduced into each column of the entire apparatus can be changed almost without limit depending on the desired product yield. The aspect of the flow can be modified to efficiently control any recycle flow to obtain the desired product. Some effluent streams can be returned to different optional process equipment at different times.

High effluent streams of glucose content are commonly used to obtain additional fructose by the isomerization method. Some effluent streams, currently containing about 12% fructose, 72% or more glucose, and 6% polysaccharides with 18-19% dry solids, are returned to the isomerization process. Outflow streams rich in polysaccharides may be directed to a glucoamylase enzyme conversion device. These effluent streams are further broken down, partly to the isomerization process and partly to the glucoamylase enzyme conversion device. It is also possible to further refine these spilled by-products and sell them for lower sweeteners and other uses.

The method of the present method for separating mixed sugar solutions provides an improved and commercially viable system for yielding high fructose sweeteners from corn starch.

Representative in application, it is believed that products containing 55-65% fructose are almost equivalent to sugar sweeteners and competitive in cost.

Corn is cultivated over a very large area and is substantially more productive than sugarcane, providing a stable supply and purchasing of raw materials at a stable price.

In contrast, sugar cane and sugar beet are subject to weather and political conditions, and the supply of sugar is highly variable.

The process method described and the apparatus used so far are obtained from corn starch by column separation of mixed sugars containing both fructose and glucose, which can produce a series of sweeteners that are competitive with sugar sweeteners. In some cases these products are more advantageous than economic ones.

Large diameter, densely packed continuous separation columns can continue to operate at high production rates and can be adjusted as needed to yield 55-99% fructose from feeds containing 40-50% fructose and glucose can do. The densely packed separation columns provide excellent separation of sugars without the need for internal controls or flow redistribution structures, because the densely packed adsorbent beds allow for the drift of liquid flowing through the continuous separation column, “front run,” This is because it is not affected by other irregularities.

Claims (1)

In a method of separating one of the components constituting it from a mixed liquid feed stream consisting of several substances into a liquid having a higher concentration than the mixed liquid feed stream, one of these materials contains an adsorbent having a selective affinity. Alternating passage of liquid feed and eluting liquid flows through a separation column comprising a chamber in which the concentration of one of these materials results in a higher outflow flow Collect the continuous portions of the effluent stream separately, first mixing this adsorbent with an excess of concentrated reagent that can expand when the adsorbent shrinks in the presence of the reagent and the concentrated reagent is removed and then sealed to the chamber of the separation column. The adsorbent by removing excess concentrated reagent from the reduced volumetric adsorbent Window to ensure that the adsorbent is completely, densely and uniformly filled through the separation column chamber while eliminating drift and turbulence to promote uniformity of flow rate across the column chamber as the fluid flows through the column. Characterized in the chromatographic separation method of fructose / glucose.

Images