FI58942C - FOERFARANDE FOER ATT FRAMSTAELLA CONVERTERS SOCKER PRODUCT - Google Patents

Description

ΓΓΤΐΙ '·' -! Γβ1 PHO TOGRAPH B Y c ö ^ Α _ 4 & Α ^ UTLÄGGNINGSSKRIFT 5 8 9 4 2 C Fater. + ti EySnnetty Π 05 1981 ^ 7 Patent rnr.idelat ^ τ ^ (51) Kv.ik.3 / inta.3 C 12 P 19/1 ^ FINLAND I — FI N LAND (21) iwttmi «wmu.-h« «» Tii »efcnfc. * 3925/73 (22) H» kuml * ptivf - An * öknlnj »d» g 19 * 12.73 ^ ^ (23) AlkupUvl — Glltl | h «udt | 19 * 12.73 (41) Tullut | ulklMk »l - Bllvlt offundlg 20.06.75 r.klrterih.llltu. (44) NlhtfcriUulpunon I »mm. | UlluU« in date. - ^ Q.

Patent · och ragictantyralaan '7 Ameion utitgd och uti.tkriftun pubitcmd ju. ux. ox (32) (33) (31) Claim claimed — Begird prloritet (71) A.E. Staley Manufacturing Company, Deleware, Decatur, Illinois, USA (72) Roy Fred Larson, Decatur, Illinois, Almerin Willard Turner, Hamshire,

The present invention relates to a process for the preparation of converted sugar products which are substantially free of recrystallized starch, Illinois, USA (US) (7 * +) Oy Heinänen Ab (5I +) A process for the preparation of converted sugar products the process involves partial hydrolysis of the starch slurry and dilution of the resulting starch or partial hydrolysis by using up to 40 units of <= <-amylase for each 10 g of solid constituents of the starch hydrolyzate.

Prior to converting the starch aqueous slurry to a syrup, the saccharification enzyme tends to gelatinize and thin the starch slurry. Gelatinization and thinning of the starch is usually performed by heating the aqueous slurry to a temperature above the gelatinization temperature of the starch and partially hydrolyzing the dissolved starch with either acid and O 2 -amylase.

In a conventional acid enzyme process, the starch slurry is hydrolyzed and diluted in the pH range of about 1.8-2.5 at elevated temperature and pressure to DE 15-20 (DE - Dextrose equivalent, i.e. reduced amount of 11 micrograms of sugar as dextrose multiplied by 2,58942 divided by mi 11gram number1 la). The diluted starch (often referred to as dissolved starch) is then usually cooled to a temperature of about 60 ° C and a pH that promotes the activity of the saccharification enzyme. An appropriate amount of saccharification enzyme is then added and the precipitation is allowed to proceed until the desired degree of syrup conversion is achieved. When it is desired to prepare a conversion syrup with a high sugar content, the saccharification is allowed to complete, after which the saccharification hydrolyzate is filtered and further processed. In the preparation of conversion syrups with a high dextrose content, the highest achievable conversion by the acid-enzyme process is usually about 95-96 D.E.

As a result of several issues due to the hydrolysis or agitation of the aqueous starch slurry, recourse has increasingly been made to processes in which the partial hydrolysis and dilution steps have been performed with an enzyme (i.e., an enzyme-enzyme process). The general method of diluting with an enzyme is performed by treating the starch with water at an pH of about 5.5-7.0, a temperature of about 80-90 ° C and 1-3 hours. After dilution with enzyme, the hydrolyzate is cooled to an enzymatic saccharification performance temperature, as in acid-enzyme processes. Compared to the acid-enzyme process, the enzyme-enzyme process results in higher yields of sugar conversion products and a reduction in the amount of certain undesired products such as ash, 5-hydroxymethylfurfural (HMF) and color-causing contaminants.

Unfortunately, the filtration of conversion sugars or saccharised sugars conventionally made from enzyme-diluted hydrolysates fails at higher filtration rates due to the starch precipitating (e.g. often only 1-2% by weight or less of solids). It has been found that, in general, enzyme-diluted starch hydrolysates tend to form precipitated starch hydrolysates (i.e., water-soluble microcrystalline particles having a β-type X-ray diffraction pattern). In addition, a starch hydrolyzate containing precipitated starch cannot be hydrolyzed efficiently and economically by enzymes.

3,58942

Several ways have been proposed to avoid starch precipitation in conversion syrup. U.S. Pat. 3 37-462 to Denault LJ et al., Applicants suggest that the precipitation problem can be alleviated by performing dilution with PKj in the presence of water-soluble calcium and sodium compounds at a temperature of about 85-91 ° C. British Patent 1,157,515 to Kroyer K. proposes solving the precipitation problem using the initial step of the partial acid hydrolysis step, in which the starch slurry is hydrolyzed to DE of not more than 10 (e.g. 5 min at 140 ° C at pH 1.8-2.5). The partial ishaohohydrolyzate is then neutralized and rapidly cooled to the enzyme liquefaction temperature and diluted.

Another proposed way to solve the precipitation issue is to dilute the starch with an enzyme, after which the hydrolyzate diluted with the enzyme is treated by boiling or autoclaving to dissolve the insoluble parts therein. The saccharification is then performed by autoclaving or boiling the treated hydrolyzate with the addition of enzyme to replace the enzyme de-activated by heat treatment (e.g., see "Diastase 73" Tech. Bull. SP-254 (11/53), Rohm & Haas Company, and Japanese Patent No. 1529 of 1964). , Iwazawa T. et alii). U.S. Pat. 3,280,006 to Hurst T.L. et Alii, it has been suggested that the precipitation problem can be solved by heating a partial hydrolyzate containing? -amylase to 90-100 ° C to dissolve substantially all of the starch followed by heat treatment above 125 ° C under pressure and subsequent saccharification with amyloglucosidase. Canadian patent no. 753 228, Wilson A.L., suggests another way to solve the precipitation problem. According to the Canadian patent, the starch slurry is converted to a paste in a steam heater at a temperature of 54-71 ° C. Precipitation of paste-like starch is prevented in the Canadian patent by diluting paste-like starch with diluted and partially precipitated starch hydrolyzate 11a. According to the Canadian patent, it is preferable to cool the pasty starch rapidly before dilution, despite the fact that the dilution step can be used as a means of cooling the pasty starch. In addition to these, attempts have been made to solve the precipitation problem in U.S. Pat. in patent no. 3,551,273. This patent proposes converting an enzyme-containing starch slurry to a paste and diluting the heated slurry continuously at 95-110 ° C for a time sufficient to convert the slurry to a paste and deactivate it without substantially deactivating the enzymes.

58942

When the heated slurry contains the remaining viable enzyme, the slurry is then immediately and continuously cooled and diluted to the desired viscosity with the enzyme at 77-91 ° C.

U.S. Pat. No. 3,654,081 further discloses a process in which starch is hydrolyzed by adding calcium or sodium salts to an aqueous starch slurry by heating the slurry and adding C? -Amylase thereto in two steps. However, the present method requires so much β-amylase that the method is expensive on an industrial scale.

Despite the time, effort, and money spent to solve the problem of starch precipitation (as has still been stated), there is still a need to prevent starch from precipitating effectively and economically. The main emphasis in attempts to solve the precipitation problem by enzymatic dilution and enzymatic saccharification has been in dissolving the partially diluted hydrolyzate precipitates by heat treatment, after which c <-amylase has been added to replace the main deactivating enzyme of the heat treatment so that The saccharified product is characterized by a slow infiltration rate as the amount of ex'-Amy glass required increases at the same time. In this case, both the process equipment costs and the total production costs increase. Alternative proposals where additional use of the enzyme is not necessary are often inappropriate for various reasons, such as expensive accessories, inefficiencies in production and scarcity of catches, and / or the formation of unwanted by-products and the like.

It is an object of the present invention to provide an improved method for thinning starch with amylase under conditions such that the amount of insoluble matter can be kept as low as possible.

It is also an object of the present invention to optimize the enzymatic activity of ° C-amylase in the hydrolysis of starch-containing substances.

It is an object of the present invention to further reduce the amount of enzyme required to dilute and saccharify starch-containing substances.

58942

It is an object of the invention to further develop a process for the preparation of a conversion syrup which can be filtered rapidly.

It is a further object of the invention to provide conversion syrups having a D.E. are high and easy to filter and perform.

It is a further object of the present invention to reduce the time required to prepare thinned hydrolysates.

Finally, it is an object of the invention to provide a more efficient and uniform process for diluting and saccharifying hydrolysates without substantially deviating from conventional production conditions and means.

The accompanying drawing shows the time and temperature conditions immediately after the initial treatment of the partial hydrolysates as described by the temperature curves.

The process according to the invention is characterized in that a) the aqueous starch slurry is partially hydrolysed at a pH of 3.6-6.5 by heating the slurry under overpressure at a temperature of at least 120 ° C to form a partial starch hydrolyzate substantially free of insoluble starch granules and DE is less than 2.0 and the viscosity is less than 20,000 cPs, after which the pH is adjusted to 5.8-8.5 and the temperature to 93-100 ° C; b) partial hydrolyzate of starch is hydrolyzed still more by the prior ° <T-amylase so that the required kokonaishydrolyysissä aamylases added either wholly or in part at this point, and allowing hydrolysis to proceed after the 93-100 ° C for at least half a minute; c) preparing the diluted hydrolyzate by gradually cooling the hydrolyzate to a temperature between 85 ° C and 93 ° C and allowing the hydrolysis to proceed by amylase to a DE of at least about 5 so that the diluted hydrolyzate does not give a blue or purple color in the starch iodine test; saccharifying the saccharifying enzyme with a preparation, preferably a glucoamylase preparation.

r '58942

The saccharified or conversion sugar prepared from this diluted hydrolyzate shows significantly increased filtration rates compared to sugars prepared from conventional enzyme-diluted hydrolysates. Significantly increased filtration rates are achieved because the thinning process of the present invention provides a thinned hydrolyzate in which the amount of starch precipitated during thinning and subsequent saccharification can be maintained at a nominal and / or substantially free non-precipitated level. As a result, conversion syrups made from this diluted hydrolysates are substantially free of precipitated starch. The present invention optimizes both the efficiency of amylase in thinning starch-containing materials and the enzyme preparation used for saccharification of thinned hydrolysates. In this case, the amount of enzyme required for both dilution and subsequent saccharification can be substantially reduced thanks to the present invention. The diluted hydrolysates can then be easily obtained from aqueous starch slurries rich in solids (e.g. 25-40% by weight solids) without further processing being necessary. Thus, dilute hydrolysates of a high solids substance can be used directly for enzymatic saccharification to produce a high sugar sugar conversion syrup. Since these diluted hydrolysates can be used directly for the subsequent enzymatic precipitation, the need for a costly evaporative process and / or additional process equipment is avoided when treating the diluted hydrolysates (or saccharified sugars).

The diluted hydrolysates prepared according to the invention can be made into a saccharified product with improved quality and improved yields. The overall process cost is competitive with the cost of conventional acid-based dilution processes, as this process can avoid filtration and precipitation issues that have been a nuisance in previously known enzyme dilution processes. The desired composition and properties of the resulting conversion syrup are more easily controlled by the dilute hydrolysates of this invention. Unlike acid enzyme processes, the process of this invention allows for high yields of sugar conversion products without the concomitant availability of unwanted by-products such as HMF, ash, colorants, and the like. According to the present invention, many different sugar conversion products can be prepared. * 7 58942

Sugar conversion products which are substantially free of precipitated starch and whose composition and sugar content have been determined can be readily obtained by using a suitable saccharification enzyme and the conditions necessary to obtain the desired conversion syrup. If desired, thinned hydrolysates can be used to prepare various conversion sugar products, such as maltose-rich sugars and syrups and syrups with high or low D.E., high or low dextrose syrups, and the like, as well as these intermediates.

In preparing the diluted hydrolyzate of this invention, a partial hydrolyzate is first prepared having a D.E. is less than 2.0 and is substantially free of insoluble starch granules. An aqueous starch slurry prepared by conventional means with a suitable pH and starch content and homogeneous is a useful starting material for the preparation of dilute hydrolysates. The starch content of the starting starch slurry may vary within relatively wide limits (e.g. 5-50%). In order to minimize the total investment and operating costs of evaporation costs in the production of saccharified sugar products, the starch slurries used as a starting material in this invention contain at least 25% by weight of starch solids and suitably about 30-40% by weight. Aqueous starch slurries with higher concentrations (e.g., greater than 40%) can be used, but are more difficult to handle from continuous operation. Unless the diluted hydrolysates have been prepared by the acid dilution technique, the pH of the aqueous slurry used to prepare the partial hydrolyzate is maintained in the range of about 3.6-5.5. The partial hydrolysates thus prepared usually have a viscosity of less than about 3000 cps but more than 200 ops ·, so that the best results are obtained with a viscosity of less than about 500 cps (determined with a "Brookfield" viscometer, 20 rpm, revolution / 1.95 ° C, pH 7.01.

The thinning method of the present invention is suitable for preparing thinned hydrolysates from various starch-containing materials. Starch-containing materials can be obtained from a variety of sources, including substantially pure starch and crude starch-containing materials. Thus pure and raw starch from corn, wheat, potatoes, sago, milo, sweet potato, Tapio sauce, sorghum, rice, beans, oats ,. arrowroot, 8,58942 barley, mixtures thereof and the like, can be used as starch-containing substances. Likewise, various fractions from both wet and dry milling processes, such as starch solutions, whole milled corn, corn flour, brewers, air-graded wheat-starch products, wet-milled fractions from grain milling, e.g., centrifugally graded, and sterilized mills, can be used in milled mills. The invention is particularly useful in preparing a thinned hydrolyzate from substantially pure commercial unmodified granular starch products (e.g., unmodified corn starch granules).

The present invention makes it possible to prepare a partial hydrolyzate from the original starches without the need for alkali or alkaline earth metals. The preparation of a partial hydrolyzate free of alkali or temporal earth metals is advantageous because such additives are then removed from the syrup (e.g. usually an ion exchange resin11a) before it is sold. Aqueous slurries of original starches which are substantially free of additives (for example, aqueous starch slurries containing less than 0.003 moles of alkali metals or alkaline earth metal compounds, such as calcium and sodium urea and, hypophosphate and, lactates, chlorides, hydrochlorides, , bicarbonates, carbonates, citrates) can be used. The amount of alkaline earth metals and alkali metals in the aqueous slurry is then preferably less than about 0.002 moles and suitably less than about 0.0015 moles.

The first step in preparing the dilute hydrolysates of this invention is to treat an aqueous starch slurry having a pH of about 3.6 to 6.5 at a temperature of at least 120 ° C under an overpressure for a time and under conditions sufficient to effect partial hydrolysis. Pressure, temperatures, pH. and other process conditions that are either too strong or too weak to provide a partial hydrolyzate of the type described above (e.g., unsuitable D.E. and mixing with insoluble starch granules) cause a natural tendency to precipitate in the diluted hydrolyzate. A significant improvement in process efficiency and ease (saccharification and sugar production) is achieved when the partial hydrolyzate is diluted to D.E. less than 1.0 Å * ′ ′ 58942 and having a viscosity in the range of about 400-1000 cps. when the resulting partial hydrolyzate D.E. is less than 0.5 (usually about 0.05-0.4), thinned hydrolysates are obtained which have significantly better properties than partial hydrolysates with a higher D.E.

A suitable processing temperature, pressure and time for this partial hydrolyzate is obtained by treating the aqueous slurry in a device commonly known in the art as a steam jet heater or jet heater in which pressurized steam is injected into the aqueous slurry of starch granules and mixed with it in the digester neck. In contact with the sprayed steam, the starch granules are heat-treated throughout and momentarily under turbulent conditions, whereby the starch granules gelatinize and dissolve. Examples of steam jet heaters in which pressures, temperatures, and feed rates can be adjusted to match the desired partial hydrolyzate are disclosed in U.S. Patents 2,805,995, 3,197,337, 3,219,483, and 3,133,836. such as a coiled tubing or pressure vessel designed to minimize fluid orientation. Other thinning equipment (e.g., heat exchangers, homogenizers, thinners, chain cookers, etc.) may be used so that the handling and process conditions are adequately controlled and the partial hydrolysates described herein are obtained.

The preparation conditions necessary to obtain a partial hydrolyzate are highly dependent on the solids content of the aqueous slurry, the nature of the starch and the pH of the aqueous slurry as well as factors such as pressure, temperature and turbulence in the preparation of the partial hydrolyzate. With regard to steam jet heaters, it is usually suitable to use relatively high pressures (e.g. 3Θ0-690 kPa) at temperatures substantially above 120 ° C in the pH range of about 4.0-5.0 with a solids content of about 30-40%. When the aqueous slurry has a relatively low solids content and pH, the partial hydrolyzate is usually prepared under less stringent process conditions than slurries having a higher solids content and pH.

10,58942

As can be seen from the above, the necessary manufacturing conditions for the preparation of the partial hydrolyzate vary considerably. Thus, the manufacturing conditions in some type of device may vary considerably. When using a steam jet heater and a reaction space, partial hydrolysates can be suitably prepared under the following conditions: (a) solids content of the aqueous slurry 25-40% by weight (b) slurry pH 3.6-6.5 (c) steam jet heater used at a temperature of about 1 to 1e 143-153 ° C and at a corresponding pressure of about 390-660 kPa (absolute) and (d) a residence time of about 1-20 minutes at a temperature of at least 120 ° C. during which the product is pressurized in the reaction space.

To prevent precipitation, more precise and efficient monitoring of the preparation is performed when an aqueous slurry having a solids content of about 30-40% by weight is passed to a steam jet heater at a temperature of about 154-160 ° C at a vapor pressure of about 530-620 kPa (absolute). at about 4.0-4.5 and the product is allowed to remain in the reaction space above 120 ° C under overpressure for an additional 4-15 minutes (suitably about 6-10 minutes).

The properties of the partial hydrolyzate are more emphasized if the treated starch is removed from the reaction path by means of excess steam through the mouthpiece to a substantially lower pressure state. A suitable way to do this is to remove the excess starch paste through the mouthpiece with steam in a space where the ambient air pressure and temperature prevail and cool the paste. Excess steam, pressing through the mouthpiece along with rapid cooling of the paste (usually to a temperature of about 93-100 ° C) effectively dissolves the starch and contributes to the non-precipitation of the starch paste.

In the preparation of partial hydrolysates, the pH of the aqueous slurry and its solid starch content have an effect on its viscosity. At a given concentration of solid starches, the viscosity of the partial hydrolyzate is logarithmically dependent on the pH of the aqueous slurry of the starch from which it is prepared. For example, the Brookfie 1d viscosity (at 95 ° C) of a few steam-heated starch aqueous slurries with a dry starch content of 30-31% is as follows: \ 11 58942 pH rotates rpm viscosity (cps) 3.6 2 20 220 4.0 2 20 420 4.5 2 20 - 750 5.0 2 10 3000 5.5 2 5 7500 6.2 6 20 20000

Csittahydrolysate having a viscosity of 20,000 cps or higher cannot be effectively utilized in commercial starch thinning processes using a conventional thinner. Although the viscosity of the resulting partial hydrolyzate can be reduced by using an aqueous starch slurry with a lower solids content, it is highly desirable in a commercial process to prepare a partial hydrolyzate having a solids content of more than 25% by weight, and in particular a hydrolyzate with more than 30% solid starches.

In this case, it is desirable to initially use an aqueous slurry with 30-35% solid starches, the pH at which it is prepared should be less than 6.0 while significant advantages in preparation and dilute hydrolysates are obtained when the pH is less than 5.5 (e.g. 7500 cps.). In the preparation, a pH lower than 5.0 results in particularly preferred partial hydrolysates for use in the present invention.

Treatment <P ^ -amy glass 1 la

In the present invention, it is essential that the partial hydrolyzate which D.E. is less than 2.0, is treated and hydrolyzed with amylase at a temperature of at least 93 ° C. Generally, it is undesirable to initially treat the partial hydrolyzate at a temperature of o β-amylase 1 Ia and process conditions that substantially inactivate the enzyme at an elevated temperature (e.g., about 110 ° C), the treated partial hydrolyzate should be rapidly cooled to a lower temperature to prevent enzyme activation. The treatment step of amylase 11a at elevated temperature results in a partial hydrolyzate in which the o / amylase can effectively dilute the hydrolyzate without further precipitation. Unsuitable process conditions following the formation of the partial hydrolyzate, but before treatment with cK-amylase, can sufficiently modify the partial hydrolyzate so that it does not have the necessary properties to prevent the precipitation of starch. In this case, after the formation of the desired partial hydrolyzate, but before the addition of the amylase, the process conditions should be maintained so as to retain the nature of the partial hydrolyzate.

An effective way to preserve the nature of the partial hydrolyzate is to interrupt or slow the hydrolysis prior to treatment with o-amylase. The interruption or retardation of the hydrolysis can be effectively controlled by cooling the partial hydrolyzate to 100 ° C and adjusting the pH to between 5.8 and 8.5. Cooling of the partial hydrolyzate can be easily accomplished by releasing the product at atmospheric pressure. The pH adjustment can be performed immediately before or immediately after cooling the partial hydrolyzate to below 100 ° C. However, it has been found that the most effective way to complete the hydrolysis is to perform pH adjustment immediately prior to cooling while the partial hydrolyzate is maintained at a temperature above 120 ° C under overpressure. Any neutralizing base that does not significantly inhibit the enzymatic activity of β-amylase (e.g., alkali and neutralizing bases of alkaline earth metals such as sodium hydroxide, sodium and calcium carbonates and bicarbonates, calcium hydroxide, etc.) can be used to adjust the pH. If salts or alkalis other than calcium ions are used to adjust the pH, conventional amounts of calcium ions should be combined with the partial hydrolyzate to maintain maximum viability of the enzyme. The purpose of a partial hydrolyzate having the above-mentioned essential properties is to obtain a basic substance which can be efficiently hydrolyzed by β-amylase 11a while maintaining its characteristic hydrolyzate character.

In order to obtain these particular dilute hydrolysates, it is necessary to further hydrolyze the partial hydrolyzate by treating it with an α-amylase (e.g. usually at least half of the total amount of 'X-amylase' used for thinning) at pH conditions favorable to hydrolysis at least after hydrolysis. 93 ° C. Such treatment not only prevents precipitation but also provides a means to significantly reduce the total amount of enzyme required. If the partial hydrolyzate in this process step is merely cooled to a conventional dilution temperature, e.g. about 79-88 ° C and diluted, the resulting product will show significant precipitation and will require large amounts of <~ <.- Amylase α and / or conversion enzyme.

j «v> '' 13 58942

The period of time during which the partial hydrolyzate concept is c <-amy] aa at a temperature above 93 ° C depends largely on the temperature of the hydrolysis step performed with the enzyme. In general, the residence time of the c? -Amylase1la at 93-100 ° C is about 0.5-25 minutes. A residence time of more than 25 minutes can be used in this treatment with o <-amylase without precipitation when an amount of enzyme is added to the hydrolyzate sufficient to dilute the hydrolyzate. In this case, relatively high temperatures can be used in the initial hydrolysis of o <-amylase11a (e.g. 2 minutes at or above 98 ° C, 4 minutes at 97 ° C and / or 6 minutes at 95 ° C or above) in combination with the larger © <-amylase levels without significantly affecting the filterability of Satan's product. However, such additional treatment cycles readily cause inactivation of the enzyme and an increase in the total amount of enzyme required to produce the diluted hydrolyzate. At the upper temperature limit (e.g., about 99 ° C), a residence time of about 30-90 seconds is sufficient, while at about 94 ° C, about 15-25 minutes are usually required. In order to reduce the amount of enzyme required for the hydrolysis of the partial hydrolyzate while maintaining the improved properties of the diluted hydrolyzate, it is preferred to perform the hydrolysis at temperatures above 96 ° C, 95 ° C and 94 ° C for up to 2, 6 and 10 minutes, respectively. The effect of the controlled temperature on the saccharification of the diluted hydrolysates is described in more detail in the examples.

The α-amylase with which the partial hydrolyzate is further treated and hydrolyzed at a temperature of 93-100 ° C is preferably the 11β-amylase which has thinned thermal stability under the conditions prevailing in the preparation of the partial hydrolyzate. In general, those amylase preparations which are thermally stable and amylase and which are able to retain 75% of their activity when dissolved in starch for one hour at 77 DEG-8 DEG C. under optimum pH conditions for the enzyme in question can be used. Thermally stable preparations from microorganisms such as bacterial (e.g. Basillus substilis), fungal (e.g. Aspergillus oryzae), higher vegetable (e.g. thin) and animal sources can be used.

Although impure o 2 -amylase preparations can be used, purified enzyme products are preferably used because the dilution and subsequent saccharification and yield are then more easily controlled. Exemplary β-amylase preparations contain bacterial enzymes such as "Takamine HT - thousand" and "Tenase" (Miles laboratories), "Rhozyme H-39" (Rohm et Haas) and "Ban 120" (Novo Industri), and fungus -iN £ -amy laas i va Imiste such as “Clarase” (Miles Laboratories). Because the thinning steps are performed at high temperatures and during periods of favorable inactivation of the enzyme, the minimum amount of enzymes required is best achieved using bacteria. - Amy laas i va Imi s tei t a.

The amount of enzyme already treated with 1 dilute hydrolyzate can vary considerably. Because the initial steps of the process prior to enzyme treatment, and thus prior to the dilution steps (described in more detail below), prevent precipitation, the minimum amount of enzyme preparation required to dilute the hydrolyzate is significantly less than the corresponding amount of enzyme required for conventional enzyme dilution. If desired, more enzymatic amounts of ε-amylase may be used than are necessary to suitably dilute the hydrolyzate without significantly affecting the filtration properties of the saccharified products to be prepared (e.g., to increase the rate of dilution). Compared to conventional enzyme thinning processes, it has been found that the thinning method of the invention significantly reduces the amount of β-amylase required, (e.g., about 25-50% or more).

As is known, determining the amount of enzyme required by weight is not an accurate means of determining the amount of enzyme required. The amount of enzyme required can therefore best be expressed by the term unit of enzyme activity per gram of starch on a dry weight basis. One unit of amylase, as defined herein, is defined as the amount that dissolves 20 g of commercial starch starch as a 10% by weight aqueous starch slurry, calculated on the dry matter, at 75 ° C and pH 6.3 in 15 minutes into a liquid hydrolyzate from which a 50 ml sample the flow time through a standard 50 ml pipette is 40 seconds. For comparison, the estimated activities of the bacterial o-amylase preparations, determined by the standard method, are as follows:

Enzyme Activity units / g of enzyme "Rhozyme H-39" (Rohm & Haas) 650 "Ban 120" (Novo Industri) 250 "Tenase" (Miles Laboratories) 275 "Takamine HT-1000" (Miles Laboratories) 460., Y · '· Ib 58942 The amount of c> C-Amylase required to dilute the starch hydrolyzate depends mainly on the amount of solids in the starch hydrolyzate, the higher amount of solids necessitates the use of a higher amount of amylase. the amount of Δ-amylase used in the dilution step is sufficient to give a substantially non-precipitating hydrolyzate, usually the amount of β-amylase required to prepare the diluted hydrolyzate is greater than about 5.0 units ° <^ - Amylase 100 g of dry starch hydrolyzate solids If desired, more β-amylase may be used to increase the rate of hydrolysis (e.g., 50 units or more). unnecessarily because they increase the cost of the enzyme and increase the filtration issues due to enzymatic impurities such as proteins and the like. In this case, the amount of β-amylase required in the commercial process for the preparation of the diluted hydrolysates in the preparation of the desired diluted hydrolyzate is about 10 to 40 units per 100 g of starch hydrolyzate solids, preferably about 15 to 30 units. Significant reduction in the total amount of 0 <1-amylase required, process efficiency and product improvement are achieved if at least half of the amount of 0 C-amylase required is initially added to the partial hydrolyzate at 93-100 ° C. Additional benefits are obtained by adding more than 75% of the amount of Ad-amylase required for dilution in the partial hydrolyzate treatment, and preferably substantially all of the required amount of c-chramylase (95% or more) is added to the partial hydrolyzate at 93-100 ° C.

-Hydrolysis after amylase treatment

After treatment of the partial hydrolyzate with ε-amylase 11a at 93-100 ° C, the diluted hydrolyzate is prepared by cooling the hydrolyzate to 85-93 ° C. The amylase is then allowed to hydrolyze the hydrolyzate to a DE of about 5.0 or greater. In order to prevent precipitation and to optimize the efficiency of the hydrolysis clumps, the dilution of the hydrolyzate is preferably carried out by reducing the dilution temperature in at least two steps so that the temperature decrease gradually increases. Dilution tanks in which the temperatures are progressively lower than in previous dilution tanks provide a means of lowering such dilution temperatures. Temperatures of about 88-93 ° C for a period of about 30-90 minutes are usually sufficient for an intermediate step. The next 16 5894 2 dilution can be performed using temperatures of about 85-91 ° C for about 1-6 hours. The rate at which the hydrolyzate thins depends on the concentration, time, and dilution temperatures of the solids in the hydrolyzate as well as the number of cx-amylase units used. For example, a diluted hydrolyzate having a DE of about 7-13 and substantially free of precipitation can be obtained by diluting a hydrolyzate having a solids content of 32% with 25 units of c * u-amylase for about 1 hour at 91-1 ° C (i.e. in the intermediate dilution step) followed by further dilution at 88-1 ° C.

As stated above, the process conditions following the treatment with? -Amylase (e.g. at 93-100 ° C) have a weighted effect on the dilute hydrolyzate obtained and the precipitated products prepared therefrom. It has been found that, in general, a significant reduction in the conversion syrup residue in the preparation of this dilute hydrolyzate is achieved by allowing the hydrolysis to continue at a temperature above 88 ° C for at least 5 minutes or longer. By allowing the hydrolysis to continue at a temperature of at least 88 ° C for 10 minutes or longer (suitably 15-25 minutes), a conversion syrup is obtained in which the starch residue is less than 0.05%. The rate at which hydrolysis is allowed to proceed at 85-100 ° C also has a weighted effect on the properties of the diluted hydrolyzate. Rapid lowering of the temperature (e.g., 5.5 ° C below about a minute) tends to increase the residue of the conversion syrup. Using gradual or progressively increasing temperature reductions after hydrolysis with α-amylase is initiated at 93-100 ° C, the resulting hydrolyzate usually has significantly altered saccharification properties compared to the hydrolyzate prepared using higher temperature reductions. Increasing decreases in temperature can be implemented stepwise as described above (e.g., batchwise in each batch, being progressively lower than the previous temperature) or gradually and continuously lowering the hydrolysis temperatures. Although average increasing decreases in temperature of less than 1.1 ° C per minute (e.g., during the first 10 minutes after treatment with? -Amylase) indicate saccharification properties of the diluted hydrolyzate, average increasing decreases in temperature (88-100 ° C) of about 0.3 ° C per minute (suitably less than 0.14 ° C per minute) improves the properties of the partial hydrolyzate thus prepared. By carefully programming the temperature reduction rate between 17 58942 B8-10 ° C, the amount of β-amylase required can be minimized to between about 10-15 units per 100 g of hydrolyzate solids.

Saccharification of dilute hydrolysates

After dilution, the pH and temperature of the diluted hydrolyzate are adjusted to optimum for enzyme saccharification to obtain the desired conversion syrup. Depending on the desired conversion syrup, the α-amylase in the dilute hydrolyzate may be inactivated or maintained as such to enhance and / or increase the activity of the saccharification enzyme. The thinned hydrolysates prepared according to the invention are in non-precipitated form and inherently prevent precipitation under conditions of enzymatic saccharification. Conversion syrups made from diluted hydrolysates then show a significantly improved rate of infiltration compared to syrups made from diluted hydrolysates. Saccharification rates and yields increase as the amount of enzyme required for saccharification decreases while using the diluted hydrolyzate of this invention.

Converted sugar products that are substantially free of precipitated starch and have the desired composition and sugar content can be obtained directly from the diluted hydrolyzate using a suitable saccharification enzyme and the conditions necessary to prepare the desired product. In this case, conventional precipitation conditions and enzyme preparations can be used in the preparation of converted sugar products containing ingredients of the desired composition, such as dextrose, dextrin, maltose, maltodextrin, high and low molecular weight polysaccharides.

The hydrolysates of the present invention are particularly suitable for use as starting materials in the preparation of dextrose conversion syrups. In preparing such dextrose conversion syrups, any glycoamylase preparation that causes conventional diluted hydrolysates to saccharify to a dilute hydrolyzate can be used. Examples of glycoamylase preparations are (often amyloglucosidases) preparations containing enzymes derived from the microorganisms Aspergillus, Clostridium, Mucor and Rhizopus genera. Glucoamylase preparations that have been processed or modified to alter transglucosulose activity are particularly suitable for use in obtaining 18,58942 high dextrose conversion syrups. Exemplary saccharification conditions and / or glucoamylase preparations that retard transglucosulase activity are described in U.S. Patents 2,881.15, 2,893,921, 3,012,944, 2,967,805, 2,970,086, 3,329,578, 3,197,338, 3,137,639, 3,067. .108, 3,303,102, 3,047,471, 3,039,936, 2,967,804, etc. If desired, other enzymes such as amyl-1,6-glucosidase (e.g., R-enzymes-isoamylase-pullulanase, etc.) can be used to perform dilute hydrophilic conversion of rolysates to dextrose.

The amount of glucoamylase used to saccharify the diluted hydrolyzate for dextrose depends on many factors, such as (1) the potency of the enzyme preparation, (21 saccharification conditions (e.g., temperature, solids content, pH, etc.), (3) desired conversion time, and (4) enzyme costs, etc. When using conventional amounts of glucoamylase, it has been found that the total conversion time required to prepare the desired syrup is substantially reduced by using the dilute hydrolysates of this invention (e.g., about 20-30% reduction in conversion time). Depending on the desired target, conversion syrups with a dextrose content (dry ingredients) of about 90 to 6% by weight are usually obtained by saccharification of a dilute hydrolyzate of about 500 to 1000% by weight, using conventional saccharification conditions and conversion times together with a reduced dosage of Glu coamylase. glucoamylase preparation per 100 g of solids of the diluted hydrolyzate. For conversion syrups with a lower D.E. and / or dextrose content, fewer glucoamylase units and / or shorter conversion times may be used.

When using the desired glucoamylase preparation, the pH and temperature of the diluted hydrolyzate are adjusted to the optimum and the saccharification is allowed to complete. The illustrative saccharification temperature (depending on the glucoamylase preparation) is about 50-70 ° C, with the optimum temperature for most glucoamylase preparations being about 54-60 ° C. Similarly, conventional saccharification pH values of the saccharification enzyme are used (e.g., about 3.8-5.0, but usually about 4.0-4.3). Under suitable conditions, the desired degree of saccharification can be achieved in 30 to 100 hours, and a conversion time of about 60 to 72 hours is most preferred.

19 5894 2

The thinned hydrolysates according to the invention are also suitable for the preparation of conversion syrups with a predetermined and limited dextrose content and a relatively high fermentation sugar and / or oligosaccharide content. Specific conversion syrups [described in U.S. Patent 3,137.B39, Hurst T.L. et al) can be prepared from a dilute hydrolyzate via an enzyme system consisting of diastase (es im. / 2) -amylase with or without <= <- amylase) and glycoamylase. Likewise, conversion syrups with a high maltose and / or oligosaccharide content in combination with a limited dextrose content [e.g. less than 25%, most preferably less than 10%) can be obtained from dilute hydrolysates using an enzyme preparation comprising diastase (e.g. fungal α-amylase and / or β-amylase) and amyl-1,6-glycosidase (e.g. R- enzyme, isoamylase, pullulanase, etc.). Likewise, cereal syrups with varying concentrations of dextrin, maltodextrin, higher and lower polysaccharides, maltose and dextrose with a DE value of about 18-35 (e.g. for the partial hydrolysis of the production of α-amylase by partial hydrolyzate can be used. under these conditions, the diluted hydrolysates then allow the conversion syrup manufacturers to prepare a conversion syrup with a more uniform and constant sugar composition compared to syrups obtained from conventional diluted hydrolysates.

The diluted hydrolyzate allows commercial syrup manufacturers to prepare conversion syrups under poorer process conditions (e.g., fungal <= <-amylase and β-amylase) with optimum activity at a lower pH (4.5-5.0) compared to acidic syrups. thinned syrups that require a pH of 5.5 to 6.0 for maximum activity.

Example 1 A. Preparation of a partial hydrolyzate

A 32 wt% aqueous slurry made from unmodified cereal starch at pH 4.2. The slurry was pumped at a rate of 9.5 dm per minute through a steam jet heater as described in U.S. Patent 3,111,284 and operated at 158 ° C at a steam pressure of 517 kPa (absolute). The resulting paste was kept in a tube connected to a steam heater at a temperature of about 158 ° C and a pressure of about 20,58942 at about 320 kPa for about 8 minutes. Immediately before passing the paste to a vacuum condenser, it was neutralized to pH 0.5 with 3.1 molar calcium hydroxide solution. The neutralized paste was then rapidly cooled to about 99 ° C. The resulting partial hydrolyzate was substantially free of starch granules and precipitated starch. The viscosity of the hydrolyzate was 600 cps as determined on a Brookfield viscometer at 95 ° C on a rotor No. 1 operated at 20 rpm The partial hydrolyzate was analyzed by copper number experiment (Industrial Engineering Chemistry, Analytical Ed., Or 13, p. 616, Farley & Hixon , 1941] and its DE was found to be 0.4.

B. Preparation of the diluted hydrolyzate

To the obtained partial hydrolyzate was added 25 units of ε-amylase per 100 g of dry hydrolyzate solids at 96 ° C. Gradual cooling of the hydrolyzate under controlled conditions to 94 ° C, 92 ° C and 85 ° C 5, 12, 23 and 180 minutes after the addition of o-amylase ("Ban 120", Novo Industri], respectively, gave a dilute hydrolyzate with a DE of 9, 0 (Analytical Method E-26, Standard Analytical Method of the Member Companies of Corn Refiners Assoc., Inc., 3rd Ed., First Revision 52768]. The diluted hydrolyzate was substantially free of starch granules and precipitated starch, as observed when the yellow color was treated with dilute hydrolyzate by starch-iodide test Standard Analytical Method E-60.

C. Preparation of dextrose conversion syrup

Dextrose-rich conversion syrup was prepared from a dilute hydrolyzate. In preparing the conversion syrup, conventional dextrose conversion equipment was used, keeping the pH of the syrup at pH 4.0 and the temperature at 60 ° C. After 72 hours of saccharification, 900 units of glucoamylase (glucoamylase-75,

Novo Industri) per 100 g of dry hydrolyzate components, the precipitation was then supplemented by carbon treatment and filtration. The filterability of the conversion syrup was determined by adding a 400 cm sample of conversion syrup at a temperature of about 77 ° C to a Buchner funnel coated with a layer of carbon (2.32 g of carbon Darco s-51 in 100 ml of water used for the layer, filter paper 9.0 cm Whatman 2] , and was connected to a water vacuum cleaner and measured in. ai ka, which was taken to accumulate a certain unit of volume in a calibrated flask.

Based on the filtrate obtained over a given period, the conversion. . The 2-pin infiltration rate was found to be 1020 1 / m filter media per hour. The resulting conversion product was analyzed to determine the weight fraction of solids.

Buchner funnel with 5.0 g of “Hyflo” filter, filtering 250 cm 3 of conversion syrup, washing the resulting cake with 50.0 cm of water, drying the washed cake in an oven at 63-71 ° C, reducing "Hyflori" - the weight of the dry filter cake obtained and dividing this value by 3 by the weight of the dry ingredients obtained from another 250 cm volume of conversion syrup. The conversion syrup was also analyzed to determine the volume fraction of solids by centrifuging a 3 cm rack of 15 cm sample in a 15 cm centrifuge tube.

sa for 20 minutes at maximum speed in a centrifuge "Model 65Θ28 H

International Laboratory Centrifuge ".

Determination of the weight fraction of insoluble constituents gave an insoluble residue of 0.5% by weight, the amount of insoluble starch being substantially 0. In the experiment to determine the volume fraction of insoluble constituents, no detectable amount of insoluble constituents was found. According to Analytical Method E-26, the D.E. value of the conversion syrup was 98. The solids content of the dextrose was 96% as determined by Analytical Method E-24.

Example 2

Process conditions and the properties of the partial hydrolyzate, as well as the thinned hydrolyzate, are important factors in the preparation of a commercially suitable conversion syrup with a high dextrose content. This example illustrates the effect of process variables on process ease and the properties of the resulting dextrose basket version syrups in the preparation of partial hydrolyzate and dilute hydrolyzate. The AK conditions used in the preparation of the diluted hydrolysates and dextrose conversion syrups from these are shown in Table 1. The table also shows under the heading "os'it-total hydrolyzate" the physical properties of the aqueous slurry (e.g. solids content and pH), steam jet heater conditions, residence time in the reaction space under substantially the same pressure and temperature conditions as used in the steam jet heater, and pH adjustment with 3.0 molar calcium hydroxide immediately prior to rapid cooling.After neutralization, each experimental difference was rapidly cooled. and initially treated with oC amylase.

In Experiments A-K, the D.E. values of the partial hydrolysates were less than 1.0. The D.E. values of the partial hydrolysates in Experiments G and H were 0.7 and 0.5, and in Experiments I-K less than about 0.5. The viscosities of the partial hydrolysates in Experiments A, G, H, I, J, and K were 1600, 200, 200, 330, 600, and 300 cps, respectively.

The temperatures at which the test batches AK were pretreated with ε-amylase are shown in Table 2. Similarly, the α-amylase unit amounts used are also shown in Table 2 under the heading “initial treatment with α-amylase1la.” Time-temperature dependence of the first 50 per minute in each experiment are shown by the curves in the accompanying drawing.

As shown in the drawing, curve A shows a partial hydrolyzate pretreated with α-amylase at 98 ° C. In curve A, hydrolysis was maintained at 98 ° C for 1 minute after initial treatment with β-amylase. Between 1 and 3 minutes, the hydrolysis was cooled to 93 ° C for 3 to 9 minutes (after the start of the hydrolysis, exi-amylase 11a). The hydrolyzate shown in curve A was further gradually cooled to 91 ° C. The hydrolysis shown in Curve A was then gradually cooled from 91 ° C to 88 ° C. About 11 minutes after the start of hydrolysis with β-amylase, the substance shown in curve A had reached a temperature of 88 ° C. The hydrolyzate was then continuously cooled (11-39 minutes) to 87 ° C. Between 39 and 189 minutes, the δ = amylase hydrolyzate was maintained at 88-1.7 ° C, after which the pH of the hydrolyzate was adjusted to 4.0 and cooled to 60 ° C. The obtained cooled diluted hydrolyzate had a D.E. value of 9.0. Dextrose-rich conversion syrup was then prepared from the diluted hydrolyzate of Experiment A.

According to the drawing, the partial hydrolysates shown in curves B, C, D and E were initially treated with α-amylase at a temperature of about 96 ° C and gradually cooled to 95 ° C over a period of more than 5 minutes. The hydrolyzate shown in Curve B was gradually cooled to 93 ° C (8 min after initial treatment and Ikeen oc. - Amy glass 1 la).

23 58942 Curves C, D and E have the same temperature and time coordinates for 10 minutes. Each of the hydrolysates shown has been gradually cooled to 94 ° C during this time. The hydrolyzate shown in Curve C was gradually cooled from 94 ° C to 91 ° C over a period of 10-13 minutes. After 10 minute intervals, the hydrolysates shown in curves D and E were cooled more slowly, respectively, as shown in the drawing. Curves B and C; C and D; and the temperature coordinates B, C, D, and E correspond to each other at 13, 16, and 25 minutes.

Curve F shows the partial hydrolyzate pretreated with a larger amount of 1 μl <= <> amylase (43 units) at 95 ° C and cooled to below 93 ° C in 45 seconds and further gradually cooled from 93 ° C to 60 ° C. C over 45 minutes, after which the diluted hydrolyzate was saccharified under conversion conditions substantially uniform to those in Experiment A. The hydrolyzate shown in Curves G and H was initialized with β-amylase at 96 ° C, allowing both hydrolyses to proceed for two minutes. The hydrolyses shown in curves G and H were then rapidly cooled to 88 ° C and 85 ° C, respectively, and maintained at these temperatures until dilution was complete.

The - => ε · amylase temperature curves in Experiments I and 3 are consistent with each other during the first 50 minutes of hydrolysis.

The curves shown in the drawing illustrate the first 50 minutes of Experiments A-K. The desired diluted hydrolysates were obtained by further hydrolyzing the hydrolyzate with β-amylase. In Experiments H and K, the first step of dilution (e.g. after 50 minutes) was performed at 85 ° C for an additional 180 minutes (e.g. after 230 minutes of time treatment with o * -amylase). The subsequent steps used to prepare the hydrolysates are as follows:

table 1

Experiment_Temperatures ° C_Hydrolysis time over 50 min.

B 88 50-150 minutes C 88 50-132 D 88 50-132 E 88 50-120 G 88 50-180 I 91 50-60 88 60-120 3 91 50-60 88 60-120 K 87 60-180 24 58942

The D.E. values of the diluted hydrolysates obtained in Experiments A-K are shown in Table 2,

In Experiments A-K, the pHs of the diluted hydrolysates were then adjusted to 4.0 and cooled to 60 ° C. Dextrose conversion syrups were obtained by saccharification of dilute hydrolysates with glucoamylase. In Experiments A, F, G, H, I, J, and K, a conversion time of 72 hours was used, while in Experiments B, C, D, and E, saccharification was performed in 65 hours. 900 units of glucoamylase per 100 g of dilute hydrolyzate solids were used in each experiment. After the saccharification was completed, the resulting conversion syrups were analyzed for D.E., dextrose content, amount of solids (each volume fraction or weight fraction of solids 1 shown in the table).

».V '',! I b 58942 c tro o \ ° cm rx no: 0 i ... c rj QJ <r- t- O n * c I 0> *: 0: 0: 0 0 ^ wa 0: S o \ »1 ' '. VV s O ^ (0 p: 0 I Pi ϊ = 1 ^ xC xC CD O ,, Ο _ *: · -} ·· —IIII σ r-4 r-4 E ω - * - 5 m -p tj 0 I- ·: 0 ·: (0: (0 · η 0 10 Q): ω> 1 .rj o "“ J +5 <- fl

- c yj, H

03 (v, cniootocDcncoinocouD 0 o • H 3 ........... e ω co w o LnincDLntninun ^ Ln ^ tD 3 c ·

£ _ι · η oV> cncncncocncncncocDcncj! 3 CT TJ

(ΰ <0 Q) ω> c CO OCOOUI ^ i-CMCnLnOlDCO O Qi cm - ........... xc γ oE lu [\ rvaocor ^ rvrv.toi ^ rv.rv _c pi- · poq cncncncncncncncncncncn · η o'h -—--------- CO U I- • r-4 ^ + -

4j CO

-P * H

(0 O -H CO

3 (0 Pi -P 0) p ω, _ "e!

4-)>, (DOC

D) H. CO Pi (0 c ° ® _ g-

C C · (0 (0 E

OJO UJ COOlCDOtOOCMCOOCJCO r-1 · ΗΟ _c>, · ........... * H coo

> 3jO □ OlOUlUl'iOl / lNlDNN -P O

* - ^ - ΐ— * - ^ - * -: 0 0 C-i

______ _____— CL C CD

Ln! E -h -O

>, 1: (0 (0 E

r-4 -rt -rt -g r-4 QJ

m cdujIh ιηιηιηιηιηΓηιηιηιηιηιη: toE

-P 0 p; q Μτ-Γ-Γ-τ-ή-ΝΝΝΝ '· (0 -P

4J ο> - p: · η qj • H r-l 0) - (= to> 0 -p -p

: 0 E I *} 0 C I

pi 0: 0 ID -H M- S

3 I CL O m · Η O I

p OS'-1 aocncncncrjLnLnLncDUDco a) pi

r-4 0: 0 -H 0) 01010) 0) 0) 0) 0) 01010) c TJ

<r _14-) -H CO

0 · Η XZ

---------- CL -P 4-) 0 ω (T) 0 0 ΣΙ I 0 0

0 -r4 0>) —I

Li -P 0 1-10 4-) c oaocncncnocjooo E oo

3t4 ......... * Ό Ch-H

mo x ixLnLninLnccivr ^ rviv. 0 τι -p 2 —I CL (0> 1> 1 0 -H r-l jC 1— (1 4_> 4J r-4 0 0

O 0 0 Ή> n C

-H 04 3 CD T) r-i C

_p C 0 -H QJ

p 0. OOOOOOOOOC31D C-H0 Pi O

0 1—) c ........... QJ 0 Pi Pit-.

p-c qj - (- e -π aoooooocococoejtD Eco ¢ -10

-p Qi -P X N (N N N (M 3 C C 0: 0 TJ

4J 3 m TJ H -p C

0 ή 0 ocDCDtocDcDoarsirvCM pc .π>, r-ι 0 0 e 0 cl cocoaococococnqjcDT-cc) 3 0 jz · η W) 4p ^ 1, cl2 p E0 cn> 3 jC 0 3 0 0 r-4 p -r- 4 0 * rl 0 O CD ^

03CICJ 3 0 0 r-4 t- CM N

t pC · η: o O I 0 0 1 — I> 1 I I

tj jzccLm r ^ c \ ifM (\ irM (Nr ^ -rv.uDcocD 0 0 E -p lu UJ

> * hc £ lB cnLDLninLninLnLnLninLn c 0 pc 0 = o

XZ 3 Q): 0 -Η 0 · Η I Pi TJ "O

0 {/) E 3 4-) c Pi 0 >> -H O O

H c -P r-4 Q 0 -C JC

0 QJ 3 i-H Pi -P -P

4J CL 0> 1> 1 QJ 0 ψ) · γ) 0 I — I · Η - Σ -rt -P 0 -1-4 QJ 0 tol 0 Pi Ct -P 0 r-4 I—) O 0 0 ( Ν (ΝΙ! \ Ι (ΝΓΜ00000: 0.p0-P000

βφ ........... E00-r4r-4OO

r-4 4- I CMOOOOOCMCNCMCNCM: θ: 0 rl 0> i -r4 t4 ma mcnmcocomrocommcn -p £ 0: 0 £ -p +) p QJ -p>, £ P 0> 1> 1 p 4-) -H Q. I 3 I r-4 r-4 C QJ OOCDOOCDOCnOCNJO r-4 · γ4 C3 Pi P 00

: 0 -P X ...........: 0-H * r-4 ^ CC

(- r-4 CL> T'3- <T «q} - ^ 3-CTJ ^ 3-'T'T" T'T >> C00 <C <

03 I I I I I I I

j <CCDC_JQLLIU_C3X) —40 ^ r f \ l (Q 4J LO (O N

‘F

? .B

58942 □ It should be noted that the values for weight and volume fractions in the table above do not apply to substance combinations. Weight percentages refer to all insoluble matter in the conversion syrup. In this case, the amounts by weight in the tables do not only mean insoluble teashydrates (e.g., heavier molecular weight polysaccharides such as precipitated and granular starches) but also insoluble lipids and proteins (if present). Further analysis of the weight fractions of the conversion syrups of Experiments G and H showed that the corresponding heavier molecular weight polysaccharides weighed about 0.7 and 1.2, respectively. Experiments G and H gave a positive result in the starch test using the standard iodide test. In contrast, the conversion syrup of Experiment I consisted mainly of lipid material and gave a characteristic yellow color in the iodide experiment.

The "volume percent" values shown in the table more accurately indicate the concentration of more molecular weight saccharides in the conversion syrups. If the conversion syrup contains insoluble protein, the protein also precipitates with the insoluble saccharide in the centrifuge tube. Because the starch slurries used in Experiments A-K were protein-free (only traces of these were present), the volume fraction values shown in the table are not distorted by such protein.

The filterability of the conversion syrups obtained in Experiments G, H, I and J was determined with a conventional filter press and the filterability 2 was found to be 191 l, 122 l, 1020 l and 1300 l / m filter medium per minute, respectively, when filtering about 38-151 l of filtrate in 9.3 2 dm filter medium. through. The filtration rates of Experiments F and K were determined by the filtration method of Example 1 and were comparable to at least Experiment I. In Experiments A, B, C and D, rapid filtration was also used (e.g., more than 10 6 1 / m / min). Although the conversion conversion of experiments G and H was relatively high D.E. and dextrose content, these conversion syrups were difficult to filter, as indicated by filterabilitys of 4.7 and 122 l / m filter media per minute, respectively.

The thinned hydrolysates of Experiments A-D, F, and I-K (as well as the conversion syrups prepared therefrom) were substantially free of precipitated starch and starch granules. The volume and weight values of the residue in the table above show a substantial absence of non-soluble constituents. blue, red and / or brownish color indicating the presence of starch.) The diluted hydrolysates and conversion syrups of Experiments G and H gave a characteristic blue color in the iodide experiment, indicating the presence of either precipitated or insoluble starch.

The primary reason for the presence of precipitated or insoluble starch in the diluted hydrolysates and conversion syrups of Experiments G and H was due to the process conditions used to prepare the diluted hydrolyzate. A comparison of the temperature-time curves in the drawing shows that the diluted hydrolysates of experiments G and H were initially treated with β-amylase for 1 minute at 95 ° C, followed by rapid cooling and further hydrolysis at 0 ° C and 85 ° C, respectively. in experiments G and H, the diluted hydrolysates of experiments AD, F and IK were initially treated with o 2 -amylase and gradually cooled, allowing the hydrolysis to continue for an excessively long time (e.g. cf. time-temperature curves of experiments AD, F and IK in experiments G and H for the corresponding curves in the drawing.

Compared to Experiments G and H, the conversion syrup of Experiment E shows a significantly faster filterability rate. The filterability rate of the conversion syrup in Experiment E was significantly lower than the filterability rates in Experiments A-D, F and I-K. The amount of insoluble constituents in the experiment was also significantly higher than in experiments A-D, F, and I-K (e.g., cf. the volume fraction of the residue in the table). The conversion syrup of Experiment E gave a brown-red color in the iodide experiment to detect starch. The principal reason why high degree of unfiltration was not obtained in Experiment E was the inactivation of α-amylase during the first step of diluting the starch hydrolyzate, the inactivation of α-amylase could have been corrected either by lowering the temperature conditions or by increasing the amount of α-amylase used.

In Experiment F, the amount of co-amylase used to dilute the hydrolyzate was substantially higher than in other experiments in the preparation of conversion syrups with high filterability. The hydrolyzate of Experiment F differs somewhat from these experiments in that the hydrolyzate was cooled more rapidly and shortened o. i a _ o J - o x s e mo a a π 1 to obtain the desired diluted · hydrolyzate 2 8 58942. The conversion syrup of Experiment F was substantially free of precipitated starch and insoluble starch (e.g., granular starch) as well as Experiments A-D and I-K. In contrast to Experiments G and H (which contained substantial amounts of insoluble starch), the diluted hydrolyzate of Experiment F was prepared gradually and progressively at a decreasing temperature. In contrast, in experiments G and H, the temperature was rapidly lowered.

From the temperature curves of Experiments B-D and K, it can be seen that the appropriate dilution step of the hydrolyzate includes the means to substantially reduce the amount of amylase necessary to produce the desired dilution hydrolyzate. ' Experiment 0 illustrates excellent thinning conditions when it is desired to keep β-amylase at a relatively low level. The amount of cis-amylase required in Experiment C could have been reduced to well below 15 units, while preventing the formation of precipitated starch.

The dilute hydrolyzate prepared in accordance with this invention should be substantially free of starch as tested by a standard iodide test. Conversion syrups made from dilute hydrolysates which give a purple or blue color are characterized by a poor rate of filtration. The conversion rates of conversion syrups made from red or brown (preferably at least brown) diluted hydrolysates are significantly higher than those of conversion syrups made from blue and purple hydrolysates. Diluted hydrolysis, which gives a yellow color to the starch in the iodide test, gives conversion syrups with unexpectedly good filtration properties.

Example 3

Several products known in the art as "maltodextrins" were prepared in the same manner and with the same equipment as in Example 1. The aqueous slurry used to prepare the maltodextrin product contained 1500 parts by weight of solid starches, 2300 parts of water and 0.5 parts of calcium diorthophosphate. The pH of the slurry was adjusted to 3.9 using 3-N hydrochloric acid. In the steam jet and reaction rooms, steam at a pressure of 448 kPa was used. The starch paste obtained from the reaction was rapidly cooled to 1 ° C and neutralized with 1.1 parts by weight of calcium hydroxide.

58942 29

The neutralized starch paste was then pretreated with 25 units of β-amylase per 100 g of dry starch solids.

The β-amylase-treated paste was gradually cooled with the hydrolyzate obtained under controlled conditions at temperatures of about 91 ° C, 88 ° C, 88 ° C and 87 ° C for 11, 14, 16, 25 minutes, respectively, from the start of enzyme hydrolysis. The hydrolyzate was then maintained at 87 ° C for 135 minutes after initial treatment with α-amylase. A portion of the hydrolyzate was then separated. A portion (hereinafter "Sample 1") was heated to 98 ° C for a period of time sufficient to inactivate the <= <- amylase therein. The pH of Sample 1 was then adjusted to 4.0 with 3-N hydrochloric acid and the sample was filtered.

The remaining hydrolyzate was maintained at 87 ° C and treated with an additional 5.7 units of? -Amylase per 100 g of starch hydrolyzate solids 180 and 390 minutes after the initial treatment-amylase 11a. Samples 2 and 3 were taken from the hydrolyzate, respectively, and treated in the same manner as Sample 1.

The illustrative maltodextrin properties of Samples 1-3 are: _Sample 1_Nample 2_Nample 3 D.E. 13.0 14.7 17.8

Saccharide content D.P.1 0.5 0.5 0.7 D.P.2 2.4 3.6 4.6 D.P.3 4.0 6.6 7.6 D.P.4 1.6 1.9 2.9 D.P.g 4.0 4.0 4.2 D.P.g or more 87.7 83.4 81.0

All samples showed excellent leaching and maltodextrin properties. As the tabulated results show, a hydrolyzate having a predetermined DE value (e.g., those with DE values less than 30) and a high oligosaccharide content (e.g., including an oligosaccharide having a DP value (degree of polymerization) of six or more, as the main ingredient on a dry weight basis) can be easily obtained using a suitable temperature, hydrolysis time and the required amount of? 2-amylase. The method used in this example is particularly useful in the preparation of 30,58942 maltodextrins having a D.E. is about 10-22 and contains at least 75% by weight of an oigosaccharide (dry ingredients) with a G.P. of six or more. Consistent with the previously reported results, it is necessary to use a significantly lower amount of <= <- amylase than is normally required in conventional processes to prepare the desired low D.E. hydrolyzate.

. ; t

Claims (14)

1. Process For Preparation of Converted Sugar Products That Are Essentially Free from Recrystallized Starch, Partial Hydrolysis of the Starch Suspension, and Dilution with the C-amylase of the Received Partial Hydrolyzate of Starch, Using a Maximum of 40 Units for every 100 g of solid constituents in the starch hydrolyzate, a) a) the aqueous suspension of starch is partially hydrolyzed at pH 3.6-6.5 by heating the suspension in overpressure at at least 120 ° C to form a portion of starch hydrolyzate which is substantially Free From unsolved starch grains and whose DE is less than 2.0 and viscosity less than 20,000 cps, after which the pH is adjusted to 5.8-8.5 and the temperature to 93-100 ° C; b) further hydrolyzes the partial starch hydrolyzate by adding thereto First oC-amylase such that the amount of β-amylase needed for total hydrolysis is added either in whole or in part at this stage and to allow the hydrolysis to proceed at 93-100 ° C. eat at least for half a minute; c) a Thinned Hydrolyzate Prepared by cooling the hydrolyzate down to 85 ° C-93 ° C and allowing the hydrolysis to proceed under the influence of amylase to a DE value of at least about 5 such that the Thinned Hydrolyzate does not give bls or purple Staining in the starch iodine test, and d) the Thinned hydrolyzate is sugared using a Pre-sugaring enzyme preparation, Preferably a glucoamylase preparation. Process according to claim 1, characterized in that the aqueous suspension of starch is poured at pH 3.6-5.0 during the hydrolysis stage (a). Method according to claim 2, characterized in that a water suspension of starch containing at least 30% by weight of dry starch substance is used, and that the obtained Thinned Hydrolyzate has a viscosity less than 3000 cps. "4. Process according to any one of claims 1-3, characterized in that at least half of the total amount of O 2 -amyl, ash is used for the preparation of the diluted hydrolyzate to the partial hydrolyzate at 93-100 ° C. 35 5 8942 5. A process according to any one of claims 1-3, characterized in that the aqueous suspension of starch contains 25-50 wt.% Dry starch substance, that the partial hydrolyzate at stage (a) has a viscosity of about 200-3000 cps, that the partial hydrolyzate is treated. and initially hydrolyzed at 93-100 ° C for 0.5-25 minutes and the amount of β-amylase added to produce thinned hydrolyzate is less than 30 units per 100 g of solid ingredients in the starch hydrolyzate. 6. Process according to any one of claims 1-5, characterized in that the total molar concentration of alkaline earth metal and alkali metal in the aqueous suspension of starch used for the partial hydrolysis is lower than 0.003 M. 7. A process according to any one of claims 1-6, characterized in that the aqueous suspension of starch is injected into a meadow heater operating at a temperature of 143-163 ° C and a pressure of 393-662 kPa (abs.) And at least more than half of the required β-amylase is added to the partial hydrolyzate at 93-100 ° C. A process according to claim 7, characterized in that immediately after the treatment of the aqueous suspension of starch in the meadow heater, the gelatinized suspension is poured into a delay space at least 120 ° C and in overpressure for 1-20 minutes so that the obtained partial hydrolyzate has less viscosity. 1500 cPs and DE less than 1.0. 9. A process according to any one of claims 1-8, characterized in that the thinned hydrolyzate is treated with a maltase preparation and converted to conversion syrup where maltose is the main constituent. 10. A process according to any one of claims 1-8, characterized in that the thinned hydrolyzate is treated with a glucoamylase preparation and that the thinned hydrolyzate is converted to syrup with a dextrose content of at least 90% of the weight of the solid bristles.