HU191822B - Process for production of additives with etherized staech base - Google Patents

Abstract

The process of the present invention is carried out by subjecting the mole of starch or 1 mole of starch to 70-130 minutes at a temperature of from 5 to 45, 30 to 65% by weight of an alkali metal hydroxide solution. 50-100 moles of monochloroacetic acid sodium salt and 0.1-0.3 moles of water-binding agent are added to the reaction mixture in 50-100 min. After stirring for -120 minutes, the product is rested for at least 1 hour at 60-110 ° C, resting in a 60-95% flat arc humidity atmosphere, and then dried, crushed and sieved in a known manner. (11) 191822 B International Class Mark: (51) NSZO * C08B31 / 10 z ^ Taiálmán ^ Patent TSr. '* property. -1-

Description

László Nemes, MSc in Chemical Engineering, 34%, Ottó Ács, ok. chemical engineer, 41%, dr. Gyori Móri-Kőnig, M.Sc. (Chemical Engineering), 25%, Nyergesújfalu

Hungarian Viscose Factory, Nyergesújfalu (54)

Process for the manufacture of ethereal starch based additives (57) EXTRACT

The process according to the invention is carried out by treating 1 molar starch or 1 molar starch-containing material at a temperature of 5-45 ° C, 0.5-1.5 molar 30-65% by weight of alkali metal hydroxide solution for 70-130 minutes. The reaction mixture is sprayed with a mixture of 0.5-1.5 moles of monochloroacetic acid sodium salt and 0.1-0.3 moles of water scavenger in 50-100 min, in equal portions over 5 to 45 v, over 120 min while stirring resumed and the product is from 60 to 110 ^e C and 60-95% humidity environment REAL arc resting utóérterezik least 1 hour and finally dried in a known manner, crushed and sieved.

191 822

FIELD OF THE INVENTION The present invention relates to an effective process for the preparation of ether derivatives of starches of various origins in a single step solid phase.

Etherified carbohydrate derivatives are substances which are commonly used in industry and are used, for example, in the paper, textile, food industry as additives, lubricants, glidants, thickeners or adhesives.

Etherified starch derivatives are prepared by reacting the reactive hydroxyl groups of starch, which has been chemically purified or containing a greater amount of glazing agent, into an alcoholate in an alkaline medium and then etherified with mono-haloacetic acid, such as monochloroacetic acid.

Changes in the properties of the final product can be accomplished by the desired degree of control over the molecular length viscosity and the degree of etherification that determines the solubility.

Prior art starch processes are characterized in that starch alcoholate forms during etherification a ductile product which is unsuitable for further processing or formulation. This interfering technological feature is eliminated by various patented processes such that water-miscible, short-chained, structural changes in the basic material of the carbohydrate alcohol during etherification, which are transformed from a powdery state through increased swelling. alcohol, such as methanol, is prevented or reacts in aqueous medium and the product is subsequently precipitated or dried. (The above solutions are disclosed in Hungarian Patent Specification No. 158,264, U.S. Patent No. 2,599,620, U.S. Patent No. 717,275, and U.S. Patent No. 56,340).

Procedures using alcohols to prevent swelling require multi-step implementation. Heating the system, separating the precipitate from the solution, regenerating the alcohol is energy- and labor-intensive, flammable, and pollutes the environment, and requires considerable expense.

Journal of St'árke 1972 24 (4), 124-7. and Japanese Kokai Tokkyo Koho JP 82 31901 also describe the preparation of etherified starches. However, in the above embodiments, the etherification is carried out in the presence of an organic solvent by a slurry process which is expensive, expensive to recover and also has a low degree of substitution (0.28) of the product according to the Japanese patent, unlike the process according to the invention. with a high degree of substitution of 0.4-0.8.

In the process described in Japanese Patent Application No. 92 (59), only starch can be used as a starting material, unlike the process of the invention, which is suitable for etherification not only of starches but also of hard starchy materials, such as low quality bakery flours. This is because, in the process of the present invention, during the etherification and related operations, a sufficient degree of continuous withdrawal of the reaction water and a higher concentration of the reactant resulting from the heterogeneous phase also allows for the processing of lower quality raw materials. In addition, the etherification is carried out in solution under high vacuum and the reaction time of the etherification is three times the time required for carrying out the process of the invention.

The product of the process described in U.S. Patent 2,802,000 is substantially different from the product of the present invention. The etherification reaction is conducted in such a way that the etherified starch retains the particle structure of the starting material, which means that the etherification reaction can only take place on the surface of the starch particles, the inside of the particles remaining unchanged (this gives the starch character of the starch). . The degree of substitution most characteristic to the quality of the partially etherified starch obtained is not given. In contrast, the process of the present invention, as mentioned above, provides a product with a high degree of etherification, a process with a lower specific material consumption and a more economical process than the prior art process.

The process according to the invention does not have the above disadvantages, since the alcoholate formation and etherification reaction is carried out in a single step without the use of an alcohol which acts as a swelling agent.

In fact, it has been found that if the water formed in the reaction is removed or bound, the reaction becomes quicker and more efficient and not only purified starch but also starch-containing materials can be etherified. The end result of the reaction is always a solid, wet, ductile but manageable product.

According to the process according to the invention, 1 mole of starch, 2/3 mole of 45-50 wt% sodium hydroxide, 2/3 mole of monochloroacetic acid and 1 mole of starch, 2/3 mole of sodium hydroxide and (3 moles + 1 to 10 moles of anhydrous sodium carbonate) is reacted with vigorous stirring to provide a wet, but still powdery product suitable for further processing and formulation. Further processing includes completion of the reaction (post-reaction) and drying and grinding to ensure non-stick storage. Time, temperature and humidity play a role in the post-reaction.

The process according to the invention is characterized by the following reactions:

li Neutralization of monochloroacetic acid

Cl-CHj-COOH + Na ₂ CO ₃ * 2 Cl-CH ₃ -COONa + + Η ₂ O ♦ COj

2.94.5 105.9 2.116.5 62

Dehydrating agent capable of absorbing excess water of sodium carbonate,

2. Gross Reaction of Alkalization and Etherification (C _e H ₁₀ O _{0 s} ) _n + Cl-CH 3 -COONa + NaOH - * · * (C _e H ₉ O ₈ J-CH ₂ -COONa + (162L 11%, 5 40 (242) _n + NaCL + H ₂ O

58.5 18 & l (Ab-rp ülf Ol í> ⁴

Cl-CH ₂ COONa + NaOH - + HO-CH ₂ COONa + NaCl glycolic acid sodium

Reactions 1 and 2 thus generate a total of 2 moles of water, the partial or total removal of which, for example, trapping, from the mixture is an important aspect of the process of the invention. Another essential feature of the process according to the invention is the provision of the medium necessary for the movement of the reagents in the heterogeneous phase reaction to complete the etherification using all or part of the bound water and / or external source water.

191 822

One embodiment of the manufacturing technology according to the invention is shown in Figure 1.

A separate part of the manufacturing technology is the grinding and neutralization of monochloroacetic acid - for example, with anhydrous sodium carbonate, or binding of the reaction water with excess crystalline anhydrous sodium carbonate (calcined soda), storage of the reagents and introduction into the delivery system.

The alkalization and etherification can be carried out in a Z-arm shredding mixer, the jacket cooling of which is important for adjusting the viscosity of the product, generally 5-15 ° C, preferably 10 ° C. The reaction time is preferably 90 minutes. The spraying of the alkali is continuous. The rest time is at least 20 minutes. The subsequent etherification reaction is suitably conducted by the addition of the above mixture of the sodium salt of the monochloroacetic acid and the water-binding agent, preferably for 1 hour every 10 minutes, maintaining the temperature at 10-15 ° C. After 60 minutes, it is checked by titration of the free sodium hydroxide, preferably 4-5% by weight.

From the mixing reactor, the material is fed to the tray pretreatment and drying apparatus, where it is suitably tempered to 60 ° C for at least 1 hour while the warm air, 60-95% RH, is circulated with a fan to provide the post-reaction water. presence of the medium necessary for movement. The product is then preferably dried at 105 ° C for at least 3 hours.

The grinding is carried out, for example, in a hammer mill with a 1 mm mesh screen. Moisture-resistant packaging can be in sealed polyethylene or polypropylene foil bags.

The invention is illustrated by the following embodiments.

Example 1

Etherification of starch by batch process

One mole of starch was added to the jacket-cooled reactor and stirred, and 2/3 mole of 45% sodium hydroxide was sprayed from the alkali tank via a pump and atomiser. The mixture was stirred vigorously for 90 minutes while maintaining the temperature at 10 ° C with external cooling. The mixture was then allowed to rest for 20 minutes.

2/3 moles of monochloroacetic acid are mixed with 1/3 ♦ 1/10 moles of crystalline anhydrous sodium carbonate in a dry mixer. The resulting monochloroacetic acid sodium salt is added to the above reaction vessel together with 1/10 molar excess of sodium bicarbonate over 1 hour at 10 minute intervals. The temperature of the reaction mixture is maintained at 10-15 ^rf . The mixture was vigorously stirred for 60 minutes and then checked for free sodium hydroxide by trituration.

The resulting product is transferred from the reactor to a tray aftertreatment and drying apparatus, which is first heated at a temperature of at least 60 ° C for 1 hour while recirculating Na ₂ tO ₃ 10H from _the water liberated from heat to heat over the trays. and then dried at 105 ° C for 3 hours.

The dry product is chopped in a hammer mill and stored in a foil bag in a moisture resistant package.

Product Features:

degree of substitution (DS): 0.4-0.66 active ingredient (carboxymethyl starch) content: 65-70t% apparent viscosity (in 5% solution at 29X ° K at 81 sec ¹ shear rate with Rheotest viscometer): 500-2000 mPas Product appearance: white to creamy powder or granular

Example 2

Etherification of starch by continuous process

The etherification procedure described in Example 1 is repeated, except that the amount and the order of addition of the reagents are carried out continuously in a rotary tube reactor. The tubular reactor is divided into five stages in which each of the production steps is carried out in the order shown in Figure 2. In the first stage, 2/3 moles of 4.5% sodium hydroxide solution is sprayed onto 1 mole of starch. In the second stage, the starch alcoholate is formed. This section is maintained at 10 ° C by jacket cooling of the tube furnace. The alcoholate conversion time is 110 minutes. In the third stage, a mixture of the monochloroacetic acid sodium salt and 1/10 mol of excess sodium carbonate is added from the silo. Etherification Total time 120 minutes. The fourth stage of the tube furnace forms the continuous post-curing heat treatment, where the material passes through 60 ° C and 60 minutes. It traverses the final, fifth stage at 105 ° C for 3 hours to dry the starch ether. The discharge structure is connected to this tube section, from where the material is transferred to a silo, thence to a continuous mill and finally to a finished product silo. The final step of the process is the removal operation. Part of the water liberated during the process is 0.1 mole anhydrous soda, or 0.14 mole magnesium sulfate or 0.08 mole potassium aluminum sulfate, or 0.13 mole aluminum sulfate, or 0.17 mole magnesium nitrate, or the same amount of magnesium. chloride, or 0.1 molar disodium tetraborate, the same amount of sodium sulfate, or 0.14 mol sodium sulfite. Water binding results in the formation of crystalline aqueous forms of the listed compounds, i.e. MgSO ₄ .7H ₂ Q, KAI SO ₄ / g. .12 H ₂ O, Al ₂ / S0 _4/3. 8H ₂ O, Mg / NOj / j. 6 H ₂ O, MgCl ₂ . 6 H ₂ O, Na ₂ B ₄ 0 ₇ . 10 H ₂ O, Na ₂ SO ₄ . 10 HjO, Well, P ₂ O ₇ . 10 H ₂ O, Na ₂ SO ₃ . 10 H ₂ O

The product characteristics correspond to those of the product of Example 1.

Example 3

Etherification of starch by batch process, chemical water binding

The procedure of Example 1 is repeated, with the change; that the water liberated during the process is chemically reacted with water instead of 1/10 mol Na ₂ CO ₃ . With 1/2 mole of calcium oxide or 1/3 mole of phosphorus pentoxide.

The product obtained has the same characteristics as the product of Example 1.

191.822

Example 4

Etherification of starch by batch process, providing external water for post-reaction water

The procedure described in Example 1 was followed except that only 2/3 mol of anhydrous monochloroacetic acid sodium salt was added to the reactor as described there and no excess of 1/10 mol of soda was added. The resulting product is transferred from the reactor to the tray reactor and dryer. The 1 mole of water required to complete the etherification reaction in the heterogeneous phase is delivered to the material on the trays in the form of a water spray produced by a high pressure sprayer in the absence of water vapor that can be liberated from the crystalline water soda. It is important to provide a spray of close to colloidal droplets.

The product has the same characteristics as the product of Example 1.

Example 5

Etherification of starch by batch process, providing water for post-reaction partly from reaction water and partly from external source

The procedure described in Example 1 was followed except that 2/3 moles of anhydrous monochloroacetic acid sodium salt and 1/20 moles of anhydrous Na ₂ CO ₃ were added to the reactor. Half of the 1 mole of water required for the post-reaction is provided by the 60 ° C provided by the tray pretreater from the 1/20 mole of Na ₂ CO ₃ , which releases 0.5 moles of crystalline water, and the other half by water spray as in Example 7.

The product has the same characteristics as the product of Example I,

Based on the starch content of the flour, 1 mol of rice starch is weighed and proceeded as in Example 1 below.

The composition of the product is as follows:

carboxymethyl starch; 63.12% nitrogenous material: 5.04% fat: 0341% raw fiber: 0.30% NaCl ⁺ Na-glycolate: 27.201% Moisture: Product characteristics: apparent viscosity (in 5% solution at 293 ° K, 81 sec ' ¹ shear, 4.00% Rhotest): 1500-2000 mPas degree of substitution (DS): 0.55 appearance: yellowish-white, granular, powdery

material

2Q Example 8

Batch etherification of wheat flour

Example 6

Etherification of starch by continuous process, providing external water for post-reaction

The same procedure as in Example 2 also involved etherification and post-etherification in a tubular reactor, except that, as described in Example 7, only 2/3 mol of anhydrous monochloroacetic acid sodium salt was added. Anhydrous soda is not added. Therefore, in the fourth stage of the tube reactor, 1 mole of water is introduced in the form of a finely divided spray. The reaction temperatures and times are the same as described in Example 2, and the final product has the same characteristics as the product of Example 1.

Example 7

Batch etherification of rice flour

The composition of low-gluten feed wheat flour, which is unfit for human consumption, is determined. In our example, the composition is as follows:

nitrogenous matter: 7.001% fat: 1.601% crude fiber: 0.90t% carbohydrate, starch: 77.901% moisture: l2 / 60t%

Based on the starch content of the flour, 1 mol of wheat starch is weighed and proceeded as in Example 1 below.

The composition of the product is as follows: carboxymethyl starch: 63.11% nitrogen content: 4.55% fat: 0.38% crude fiber: 0.581%

NaCl + Na glycolate: 27.37% moisture: 4.00%

Product features:

apparent viscosity (in 5% solution at 293 ° K, shear strength sec ' ¹ , ·

Rheotest (measured by viscometer):

degree of substitution (DS): appearance:

Example 9

Batch etherification of rye flour

1500-200 mPas 0.5 White to yellowish, granular powder

Peeled, contaminated, human food

matt rice flour is defined as protein, cellulose, fat and starch. In our example, next: Nitrogenous substance: 7.88% fat: 0.53% raw "fiber: 0.471% carbohydrates, starches: 77.791% ash: 0.78% moisture: 12.55%

The flour has the following composition:

ash, minerals: 0.42t% nitrogen: 5.51% fat: 0.40t% crude fiber: 0.101% carbohydrate, starch: 80.58% moisture: 13.00t%

Taking into account the starch content of the flour, 1 mol of rye starch is weighed and proceeded as in Example 1 below.

191 822

The composition of the product is as follows: carboxymethylcellulose in Starch: 64.61% nitrogenous material: 3.47% fat: 0.25% raw fiber: 0.07% NaChNa glycol: 27.601% moisture: 4.001% Product Features: apparent viscosity (as in Examples 10 and 11, respectively) determined): 1500-2000 mPas degree of substitution (DS): 0.55 appearance: yellowish-white,

granular, powdery

Example 10

Continuous etherification of potato flakes

The composition of the raw material is as follows:

ash, mineral: 4.54t% nitrogen: 7.97t% fat: 0.301% crude fiber: 2.25t% carbohydrate, starch: 72.43t% moisture: 12.51t%

Taking into account the starch content of the potato flake, weigh the required reagents per mole of starch, using the ratios described in Example 1, into the rotary tube reactor mentioned in Example 1 and carry out each of the production steps in the order shown in Figure 2.

The finished product has the following composition:

carboxylmethyl starch: nitrogenous matter: fat:

raw fiber:

NaChNa glycolate:

moisture:

Product Characteristics: Apparent Viscosity (as determined in Examples 10 and 11): Institutional dues (DS): external appearance:

1500

60.16%

5.21t% 0.25t% 1.47t% 28.91t% 4.001%

-2000 mPas 0.55 yellowish-white, granular-like

Example 11

Batch etherification of maize flour The composition of the raw material is as follows:

moisture: 11.031% nitrogenous matter: 8.84% fat: 1.051% carbohydrate, starch: 78.04t% crude fiber: 0.36% ash, mineral: 0.681%

Taking into account the starch content of the maize flour, weigh the reagents required per mole of starch and continue to measure 1.

g as described in Example g.

The composition of the product is as follows:

carboxymethyl starch: 63.261% nitrogenous material: 5.591% fat: 0.661% raw fiber: 0.23% NaCl + Na-glycolate, ash 26.25% moisture: 4.001% Product features: apparent viscosity (as in previous examples Rheotest, 5% solution): 1500-2000 mPas degree of substitution (DS): 0.55 appearance: yellowish white,

granular, powdery

Claims

Claims (5)

A process for the batch or continuous production of ethereal starch based additives, characterized in that, for one mole of starch or one mole of a chimney, for a period of 70 to 130 minutes at 5 to 45 ° C, 0.5 to 1.5 moles. A solution of -65% by weight of alkali metal hydroxide is sprayed and the reaction mixture is sprayed with 0.5 to 1.5 moles of monochloroacetic acid sodium salt and 0.1 mol / l in 50-100 minutes at 5 to 45 ° C. A mixture containing -0.3 M water binder is added, the reaction is continued for 50-120 minutes with stirring, and the product is re-triturated at 60-110 ° C, 60-95% RH for at least 1 hour, finally known dried, chopped and sieved. 2. The process of claim 1 wherein the water-binding agent is anhydrous sodium carbonate. 40 3. The process according to claim 1, wherein the water-binding agent is calcium oxide or phosphorus pentoxide. A process according to claim 1, characterized in that the water required for the post-etching of the article is provided by releasing the bound water within the mixture and / or from water vapor introduced from the outside. 5. Process according to any one of claims 1 to 3, characterized in that rice, wheat, rye, maize flour or potato flakes are used as starting materials. 2 pieces of figure Published by: National Office of Inventions Responsible: Zoltán Himer KODEX -5191.822 International Classification: C 08 B Figure 31/10