PRODUCTION OF HYDROLYSED PROTEINS

Abstract: A process for the production of a hydrolysed protein which comprises hydrolysing a plant or animal protein with hydrochloric acid to give a slurry and then, before or after filtering off the residual unhydrolysed material, treating with alkali to a pH of from 8 to 14 and holding for a period of time to reduce the amount of undesirable chlorinated compounds and readjusting to a pH of from 4 to 7 to give a liquid hydrolysed protein filtrate.

Description: Hydrolysed proteins have been known in food systems for centuries in the Far East in the form of soy sauce which traditionally has been prepared by enzymatic hydrolysis requiring a long period of time, usually several months, for preparation. About 100 years ago, a more rapid method of hydrolysing proteins for producing flavours was developed using hydrochloric acid in which the time required is only a few hours. In this acid hydrolysis process, vegetable plant or animal proteins derived from corn, soy, wheat, rice, yeast, peanut or casein are commonly used as starting protein sources and are usually obtained as a result of the separation of the protein fraction during milling of grains or following solvent extraction of oils. The protein contents of these raw materials may range from 40% to 90% with a general average of about 60%. Normally, the protein source is hydrolysed with hydrochloric acid having a concentration of about 20% by weight at a temperature from about 120° - 135°C over a period from about 5 to 8 hours and elevated pressure up to 30 psig (2 bars). Following hydrolysis, the slurry is neutralised with a suitable alkaline material such as sodium hydroxide or sodium carbonate to a pH from 5.0 to 5.3 and the residual unhydrolysed material (lignin, humin) filtered out. The slurry may be decolourised prior to filtration or the filtrate following filtration may be decolourised by conventional means e.g. activated carbon, absorption resins. Following filtration of the unhydrolysed material, the dilute liquid can be concentrated to precipitate part of the salt formed and then refiltered. Afterwards, the liquid which contains about 42% solids may be further concentrated to pastes or dried by any conventional means such as spray drying or vacuum drum drying to powdered products. Thus acid hydrolysed proteins can be in either liquid, paste or powder form and are composed mainly of amino acids and salt resulting form the acid catalysed breakdown of peptide bonds present in edible proteinaceous materials. The flavour of the product will, of course, vary depending upon the type of source of protein used as the raw material. However, the use of hydrochloric acid in the hydrolysis of proteins leads to the formation in side reactions of certain undesirable chlorinated by-products such as α-chlorohydrins. There are various possible processes which may be considered for reducing the quantities of these compounds. For instance, it would be possible to use a starting material which does not contain any fats, since glycerol is one of the precursors which enables chlorohydrins to be formed with hydrochloric acid. However, on the one hand, starting materials such as these are more or less commercially unobtainable and, on the other hand, would significantly modify the organoleptic qualities of the flavour. In another possibility, hydrolysis could be carried out with a chlorine free mineral acid such as sulfuric acid or phosphoric acid. However, such a modification of the traditional process would also have adverse affects upon the organoleptic qualities of the flavour obtained. EP-A-0226769 describes the removal of chlorohydrins by steam distillation or by treatment with activated carbon. US-A-4053525 describes the production of glycerine by hydrolysing chlorohydrins with an aqueous alkaline reaction mixture at alkaline pH, but it is not obvious that this can be carried out in a mixture containing a slurry of hydrolysed protein without affecting the organoleptic properties thereof. We have developed a process for the production of hydrolysed proteins using hydrochloric acid in which the quantity of undesirable chlorinated compounds is substantially reduced without having a substantial adverse effect on the organoleptic characteristics of the hydrolysed protein product and wherein a flavour may be achieved which is substantially similar to that of a hydrolysed protein produced under normal conditions. Accordingly, the present invention provides a process for the production of a hydrolysed protein which comprises hydrolysing a plant or animal protein with hydrochloric acid to give a slurry and then, before or after filtering off the residual unhydrolysed material, treating with alkali to a pH of from 8 to 14 and readjusting to a pH of from 4 to 7 to give a liquid hydrolysed protein filtrate. Afterwards, the liquid hydrolysed protein filtrate may be concentrated to precipitate some of the salt formed and refiltered to give a liquid hydrolysed protein product. The plant or animal protein may be derived from various origins such as corn, soy, wheat, rice, yeast, peanut or casein and is usually obtained by separation of the protein fraction during milling of grains or following solvent extraction of oils. For example, it is possible to use oil seed cakes, cereal gluten or defatted soya flour. The hydrochloric acid used for the hydrolysis is preferably concentrated and may have a concentration from 15% to 25%, preferably from 16% to 22% and especially from 17% to 19% by weight. The amount of protein material may vary widely for instance, from 30 to 50% by weight, but more usually from 35 to 45% by weight and preferably from 38 to 42% by weight based on the total weight of hydrolysis mixture. The temperature of the hydrolysis may be from 70°C to 140°C, more usually from 100°C to 130°C, preferably from 105°C to 120°C and especially from 110°C to 115°C. The duration of the hydrolysis may vary from 2 to 12 hours more usually from 2.5 to 8 hours, generally longer periods of time being required at lower temperatures. Advantageously, the duration of the hydrolysis is from 3 to 7 hours, especially from 3 to 5 hours. We have found that by decreasing either the acid concentration from the normal 20% to about 18%, the temperature from the normal 120°C-135°C to 110°C-115°C or the duration from the normal 5-8 hours to 3-4 hours, or a combination of two or more of these processing parameters, the amount of the undesirable chlorinated compounds can be reduced significantly. The hydrolysis may be carried out with stirring and, if desired, under elevated pressure for instance up to 6.895 bar (100 psig) and more usually from 6.895 x 10⁻¹ to 3.448 bar (10 to 50 psig). After hydrolysis, before or after filtering off the residual unhydrolysed material, the hydrolysed protein is first treated with a food-acceptable strong alkali such as KOH or NH₄OH, but preferably NaOH and/or Na₂CO₃ to adjust the pH to from 8 to 14 and held at a temperature and for a period of time to reduce the amount of undesirable chlorinated compounds. The pH is preferably adjusted to from 9 to 13 and especially from 10 to 12 by the alkaline treatment. Generally alkaline treatments to higher pH values require shorter processing times than treatments to lower pH values because the higher the concentration ratio of (OH⁻) to the α-chlorohydrin, the faster the reaction and the greater will be the reduction in quantity of the α-chlorohydrin. In addition, at any particular pH the higher the temperature employed, the shorter the time necessary. For example, the temperature may range from ambient to 170°C or even higher if extremely short processing times are used. The time period may range from a few seconds at high pH and temperatures above ambient, to 24 hours or even several weeks or more at ambient temperatures. The actual processing time and the temperature at any given pH is dictated by the residual quantity of undesired chlorinated product and the overall desired organoleptic acceptance of the hydrolysed protein. For example, a high temperature short time treatment such as from 100° to 140°C over a period of from 1 to 5 minutes may be advantageous. The pH of the alkaline hydrolysed protein is then readjusted to a pH from 4 to 7 preferably from 5 to 5.5, with acid, usually hydrochloric acid at a temperature usually from 10°C to 50°C and preferably from 20°C to 30°C although higher or lower temperatures may be employed. The residual unhydrolysed material consisting mainly of lignin and humin is filtered off from the slurry before or after the pH adjustment. The slurry may be decolourised prior to filtration or the liquid filtrate following filtration may be decolourised by conventional means e.g. activated carbon, absorption resins. The liquid hydrolysed protein filtrate may then be concentrated, for instance, by evaporation to precipitate some of the salt formed and then refiltered to remove this precipitated salt to give a liquid hydrolysed protein product which may contain from 20% to 50%, and preferably from 35% to 45% by weight of solids. The liquid hydrolysed protein product may then be evaporated further to give a paste of about 85% by weight of solids and, if desired, the paste may be dried and ground to give a powder usually containing about 96-98% by weight of solids. The following Examples further illustrate the present invention: Example 1 100 kg of corn gluten containing about 60% protein is hydrolysed with 180 kg of 20% hydrochloric acid at 120°C for 7 hours. The resultant slurry is filtered to remove unhydrolysed material such as lignin and humin, decolourised with active carbon, and the liquid filtrate is then treated with sodium hydroxide solution to a pH of 11.5 and held at the times and temperatures indicated in the following Table I which gives the α-chlorohydrin content as a percentage. The pH is then readjusted to 5.2 with hydrochloric acid at 25°C and the liquid hydrolysed protein filtrate is then concentrated by evaporation to precipitate some of the salt formed and refiltered to give a liquid hydrolysed protein product having a solids content of 42% by weight. The product has a more rounded, less acidic character when compared with a product prepared by the normal process. It can be seen that increased holding temperatures and times lead to a greater reduction in the quantity of α-chlorohydrin, and that at higher temperatures, shorter times may be used to obtain a specific reduction in the quantity of -chlorohydrin. (ND = not detected) Example 2 The procedure in Example 1 was repeated except that the liquid filtrate treated with sodium hydroxide was held at 24°C for 14 hours at the pH values indicated in Table II which indicates the percentage α-chlorohydrin content compared with a control at a pH of 5.47. Example 3 The procedure in Example 1 was repeated except that the hydrolysis was carried out with 18% hydrochloric acid at 110°C for 3.5 hours and the liquid filtrate treated with sodium hydroxide solution to a pH of 11.5 was held at 35°C for 15 minutes. The flavour of the product was found to be very similar to normally prepared hydrolysed plant proteins. The α-chlorohydrin content was so low as to be undetectable. Example 4 The procedure in Example 1 was repeated except that the hydrolysis was carried out with 18% hydrochloric acid at 120°C for 7 hours and the liquid filtrate treated with sodium hydroxide solution to a pH of 10.5 and held at 120°C for 3.5 minutes. The α-chlorohydrin content of the product was less than 0.50 ppm.

Claims: 1. A process for the production of a hydrolysed protein which comprises hydrolysing a plant or animal protein with hydrochloric acid to give a slurry and then, before or after filtering off the residual unhydrolysed material, treating with alkali to a pH of from 8 to 14 and holding for a period of time to reduce the amount of undesirable chlorinated compounds and readjusting to a pH of from 4 to 7 to give a liquid hydrolysed protein filtrate. 2. A process according to claim 1 which comprises concentrating the liquid hydrolysed protein filtrate to precipitate some of the salt formed and refiltering to give a liquid hydrolysed protein product. 3. A process according to claim 1 wherein the concentration of the hydrochloric acid is from 15% to 25% by weight. 4. A process according to claim 1 wherein the concentration of the hydrochloric acid is from 17% to 19% by weight. 5. A process according to claim 1 wherein the temperature of the hydrolysis is from 70°C to 140°C. 6. A process according to claim 1 wherein the temperature of the hydrolysis is from 110°C to 115°C. 7. A process according to claim 1 wherein the duration of the hydrolysis is from 2.5 to 8 hours. 8. A process according to claim 1 wherein the duration of the hydrolysis is from 3 to 5 hours. 9. A process according to claim 1 wherein the hydrolysis is carried out under elevated pressure up to 6.895 bar (100 psig). 10. A process according to claim 1 wherein the pH is adjusted with NaOH and/or Na₂ CO₃. 11. A process according to claim 1 wherein the pH is adjusted to a value from 10 to 12. 12. A process according to claim 1 wherein the slurry is held at the adjusted pH at a temperature from ambient to 170°C for a period of from several weeks to a few seconds. 13. A process according to claim 1 wherein the slurry is held at the adjusted pH at a temperature from 35° to 55°C for a period of from 30 minutes to 4 hours. 14. A process according to claim 1 wherein the slurry is held at the adjusted pH at a temperature from 100° to 140°C over a period of from 1 to 5 minutes. 15. A process according to claim 1 wherein the pH is readjusted to a value from 5 to 5.5. 16. A process according to claim 15 wherein the temperature is from 10° to 50°C 17. A process according to claim 2 wherein the liquid hydrolysed protein product is further evaporated to give a paste, which may be dried and ground to a powder.

Inventors: CORNET, PAUL-EMILE, FAESI, ROLAND, NIELSEN, MILO A., SO, REBECCA SUI-CHUN, TANDY, JOHN STEWART
Applicants: SOCIETE DES PRODUITS NESTLE S.A.
Application year: 1989
Main classification: A23J3
IPC codes: C07K1, A23J3, C07K14