Process for the preparation of a low irritant acidifier for feed

Abstract

This invention discloses a method for preparing a low-irritant feed acidifier, belonging to the field of feed additives. The preparation method includes preparing fumaric acid-treated sodium lignin sulfonate, preparing glutathione-treated sodium lignin sulfonate, and mixing them to prepare the acidifier. The acidifier emulsion prepared by this invention exhibits good stability. When the stability of the acidifier emulsion is tested according to the method in GB / T1603-2001, the emulsion does not exhibit stratification or precipitation.

Description

Technical Field

[0001] This invention relates to a method for preparing a low-irritant feed acidifier, belonging to the field of feed additives. Background Technology

[0002] With the development of intensive animal husbandry, livestock diseases are becoming increasingly complex, and the use of veterinary drugs and antibiotic feed additives is increasing. The harm that antibiotics cause to animals and humans is becoming increasingly prominent. Under these severe circumstances, the European Union has fully implemented a policy of banning antibiotics in feed, and my country has also required feed production enterprises to stop producing commercial feed containing growth-promoting drug feed additives (excluding traditional Chinese medicine).

[0003] Acidifiers increase feed acidity. Their main components are formic acid, acetic acid, propionic acid, butyric acid, and their glycerides and salts such as sodium formate, potassium formate, sodium diformate, methyl diformate, and sodium diacetate. They are usually in liquid or powder form, combined with water or feed, and after ingestion by animals, they improve the digestive tract environment to meet nutritional needs and prevent disease. Initially, acidifiers were used as flavor additives to improve feed palatability. Further research has revealed that feed acidifiers also lower the pH and acid-binding capacity of drinking water and feed, while increasing the activity of digestive enzymes in the digestive tract, activating certain important enzymes (such as pepsinogen). Acidifiers also play a role in maintaining the balance of the intestinal microecology, reducing the occurrence of diseases, and promoting the digestion and absorption of nutrients such as protein.

[0004] Acidifiers, characterized by no residue, no drug resistance, and no toxic side effects, are increasingly attracting the attention of livestock producers. They can improve the digestibility and utilization of nutrients such as protein and minerals in feed, while also inhibiting pathogens, regulating the gut, and promoting growth, making them an increasingly popular alternative to antibiotics.

[0005] The addition of formates enables formic acid to associate with metal ions (or ammonium ions), effectively reducing the volatility of formic acid. However, these ions also bring some negative effects. Ammonium ions are prepared by passing liquid formic acid through liquid ammonia, and ammonia is known to be toxic to organisms. Excessive intake of sodium ions can raise blood pressure, which is detrimental to the health of organisms. Potassium is expensive, and calcium reduces the bactericidal performance of acidifiers. Sodium lignosulfonate has been added to formic acid-type acidifiers to reduce the irritation of formic acid, and the effect has been improved to some extent, but it is still not significant enough. This is because sodium lignosulfonate has low solubility in high concentrations of formic acid, which means that the formic acid-type acidifier added to feed still has a high irritant effect on livestock, and the emulsion formed by the two has poor stability. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the defects of the existing technology. By specially treating sodium lignosulfonate and combining it with tannin, an acidifier is finally prepared, which improves the stability of the acidifier emulsion while reducing its irritation to animals.

[0007] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0008] A method for preparing a low-irritant feed acidifier, the method comprising preparing fumaric acid-treated sodium lignin sulfonate, preparing glutathione-treated sodium lignin sulfonate, and mixing them to prepare the acidifier.

[0009] The following are further improvements to the above technical solution:

[0010] The method for preparing fumaric acid-treated sodium lignosulfonate is as follows: sodium lignosulfonate is mixed with deionized water and stirred until completely dissolved. Then, tris(hydroxymethyl)aminomethane and fumaric acid are added. After the addition is completed, the pH is adjusted to 7.7-8.0. Then, the temperature is controlled at 41-43℃ and stirred for 320-390 minutes. After stirring, sodium lignosulfonate is precipitated by alcohol precipitation, and then washed with alcohol and dried to obtain fumaric acid-treated sodium lignosulfonate.

[0011] The mass ratio of sodium lignosulfonate, deionized water, tris(hydroxymethyl)aminomethane, and fumaric acid is 9-11:75-85:2.5-3.5:1.7-2.3.

[0012] The method for preparing glutathione-treated lignin sulfonate is as follows: Fumaric acid-treated lignin sulfonate is mixed with deionized water and stirred until completely dissolved. Then, EDC and NHS are added, and the temperature is controlled at 1-3°C using an ice-water bath. The mixture is stirred for 14-16 minutes. Glutathione is then added, and the temperature is adjusted to 51-55°C. The stirring speed is controlled at 25-35 r / min, and the mixture is stirred for 11.5-12.5 hours. After stirring, the lignin sulfonate is precipitated using an alcohol precipitation method, and then washed with alcohol and dried to obtain glutathione-treated lignin sulfonate.

[0013] The mass ratio of fumaric acid-treated sodium lignosulfonate, deionized water, EDC, NHS, and glutathione is 9-11:90-110:1.8-2.2:3.5-4.5:2.7-3.3.

[0014] The method for preparing the acidifier by mixing is as follows: glutathione-treated sodium lignosulfonate and brassinin are mixed to obtain a mixed powder, then the mixed powder is mixed with deionized water to obtain a mixed solution, and then the mixed solution is mixed with formic acid solution to obtain the acidifier.

[0015] The mass ratio of sodium lignin sulfonate treated with glutathione to Brazilian tannin is 1:0.8-1.2;

[0016] The mass ratio of the mixed powder to deionized water is 25-35:65-75;

[0017] The volume ratio of the mixed solution to the formic acid solution is 1:0.8-1.2;

[0018] The concentration of the formic acid solution is 55-85%.

[0019] Compared with the prior art, the present invention achieves the following beneficial effects:

[0020] The acidifier emulsion prepared by this invention has good stability. The stability of the acidifier emulsion was tested according to the method in GB / T1603-2001, and the emulsion did not undergo stratification or precipitation.

[0021] The acidifier emulsion prepared by this invention has low irritation to livestock. In palatability tests on domestic pigs, the average daily feed intake of domestic pigs was increased.

[0022] The acidifier prepared in this invention can effectively prevent feed from becoming moldy. The acidifier was added to the feed at a dosage of 0.5 wt%, and then the mold growth of the feed was tested according to the method in GB / T13092-2006 after the addition of the acidifier for different periods of time. The total bacterial count of the feed on the first day was 1.2 x 10⁻⁶. 3 On day 10, the total bacterial count in the feed was 1.4-1.6 x 10^6. 3 On day 20, the total bacterial count in the feed was 3.1-3.5 × 10⁻⁶. 3 On day 30, the total bacterial count in the feed was 5.6-5.9 x 10^6. 3 On day 50, the total bacterial count in the feed was 1.6-1.8 x 10^6. 4 . Detailed Implementation Example 1

[0023] (1) Preparation of fumaric acid-treated sodium lignosulfonate

[0024] Sodium lignosulfonate was mixed with deionized water and stirred until completely dissolved. Then, tris(hydroxymethyl)aminomethane and fumaric acid were added. After the addition was completed, the pH was adjusted to 7.8. The temperature was then controlled at 42°C and stirred for 360 minutes. Sodium lignosulfonate was precipitated by alcohol precipitation, and then washed with alcohol and dried to obtain fumaric acid-treated sodium lignosulfonate.

[0025] The mass ratio of sodium lignosulfonate, deionized water, tris(hydroxymethyl)aminomethane, and fumaric acid is 10:80:3:2.

[0026] (2) Preparation of glutathione-treated sodium lignin sulfonate

[0027] Sodium fumarate treated with deionized water was mixed and stirred until completely dissolved. Then EDC and NHS were added, and the temperature was controlled at 2°C using an ice-water bath. The mixture was stirred for 15 minutes. Then glutathione was added, and the temperature was adjusted to 53°C. The stirring speed was controlled at 30 r / min. The mixture was stirred for 12 hours. After stirring, sodium lignin sulfonate was precipitated by alcohol precipitation. After washing with alcohol and drying, glutathione-treated sodium lignin sulfonate was obtained.

[0028] The mass ratio of fumaric acid-treated sodium lignosulfonate, deionized water, EDC, NHS, and glutathione is 10:100:2:4:3.

[0029] (3) Preparation of acidifying agent by mixing

[0030] Sodium lignin sulfonate treated with glutathione is mixed with Brazilian tannin to obtain a mixed powder. The mixed powder is then mixed with deionized water to obtain a mixed solution. The mixed solution is then mixed with formic acid solution to obtain an acidifying agent.

[0031] The mass ratio of sodium lignin sulfonate treated with glutathione to Brazilian tannin is 1:1.

[0032] The mass ratio of the mixed powder to deionized water is 30:70;

[0033] The volume ratio of the mixed solution to the formic acid solution is 1:1;

[0034] The concentration of the formic acid solution is 85%. Example 2

[0035] (1) Preparation of fumaric acid-treated sodium lignosulfonate

[0036] Sodium lignosulfonate was mixed with deionized water and stirred until completely dissolved. Then, tris(hydroxymethyl)aminomethane and fumaric acid were added. After the addition was completed, the pH was adjusted to 7.7. The temperature was then controlled at 41°C and stirred for 390 minutes. Sodium lignosulfonate was precipitated by alcohol precipitation, and then washed with alcohol and dried to obtain fumaric acid-treated sodium lignosulfonate.

[0037] The mass ratio of sodium lignosulfonate, deionized water, tris(hydroxymethyl)aminomethane, and fumaric acid is 9:75:2.5:1.7.

[0038] (2) Preparation of glutathione-treated sodium lignin sulfonate

[0039] Sodium fumarate treated with lignin sulfonate was mixed with deionized water and stirred until completely dissolved. Then EDC and NHS were added, and the temperature was controlled at 1°C using an ice-water bath. The mixture was stirred for 14 minutes. Then glutathione was added, and the temperature was adjusted to 55°C. The stirring speed was controlled at 25 r / min and the mixture was stirred for 12.5 hours. After stirring, sodium lignin sulfonate was precipitated using an alcohol precipitation method. After washing with alcohol and drying, glutathione-treated sodium lignin sulfonate was obtained.

[0040] The mass ratio of fumaric acid-treated sodium lignosulfonate, deionized water, EDC, NHS, and glutathione is 9:90:1.8:3.5:2.7.

[0041] (3) Preparation of acidifying agent by mixing

[0042] Sodium lignin sulfonate treated with glutathione is mixed with Brazilian tannin to obtain a mixed powder. The mixed powder is then mixed with deionized water to obtain a mixed solution. The mixed solution is then mixed with formic acid solution to obtain an acidifying agent.

[0043] The mass ratio of sodium lignin sulfonate to brassinin treated with glutathione is 1:0.8.

[0044] The mass ratio of the mixed powder to deionized water is 35:65;

[0045] The volume ratio of the mixed solution to the formic acid solution is 1:0.8;

[0046] The concentration of the formic acid solution is 70%. Example 3

[0047] (1) Preparation of fumaric acid-treated sodium lignosulfonate

[0048] Sodium lignosulfonate was mixed with deionized water and stirred until completely dissolved. Then, tris(hydroxymethyl)aminomethane and fumaric acid were added. After the addition was completed, the pH was adjusted to 8.0. The temperature was then controlled at 43°C and stirred for 320 minutes. Sodium lignosulfonate was precipitated by alcohol precipitation, and then washed with alcohol and dried to obtain fumaric acid-treated sodium lignosulfonate.

[0049] The mass ratio of sodium lignosulfonate, deionized water, tris(hydroxymethyl)aminomethane, and fumaric acid is 11:85:3.5:2.3.

[0050] (2) Preparation of glutathione-treated sodium lignin sulfonate

[0051] Sodium fumarate treated with lignin sulfonate was mixed with deionized water and stirred until completely dissolved. Then EDC and NHS were added, and the temperature was controlled at 3°C ​​using an ice-water bath. The mixture was stirred for 16 minutes. Then glutathione was added, and the temperature was adjusted to 51°C. The stirring speed was controlled at 35 r / min and the mixture was stirred for 11.5 hours. After stirring, sodium lignin sulfonate was precipitated by alcohol precipitation. After washing with alcohol and drying, glutathione-treated sodium lignin sulfonate was obtained.

[0052] The mass ratio of fumaric acid-treated sodium lignosulfonate, deionized water, EDC, NHS, and glutathione is 11:110:2.2:4.5:3.3.

[0053] (3) Preparation of acidifying agent by mixing

[0054] Sodium lignin sulfonate treated with glutathione is mixed with Brazilian tannin to obtain a mixed powder. The mixed powder is then mixed with deionized water to obtain a mixed solution. The mixed solution is then mixed with formic acid solution to obtain an acidifying agent.

[0055] The mass ratio of sodium lignin sulfonate treated with glutathione to Brazilian tannin is 1:1.2.

[0056] The mass ratio of the mixed powder to deionized water is 25:75;

[0057] The volume ratio of the mixed solution to the formic acid solution is 1:1.2;

[0058] The concentration of the formic acid solution is 55%.

[0059] Comparative Example 1

[0060] (1) Preparation of glutathione-treated sodium lignin sulfonate

[0061] Sodium lignosulfonate was mixed with deionized water and stirred until completely dissolved. Then EDC and NHS were added, and the temperature was controlled at 2°C using an ice-water bath. The mixture was stirred for 15 minutes. Then glutathione was added, and the temperature was adjusted to 53°C. The stirring speed was controlled at 30 r / min. The mixture was stirred for 12 hours. After stirring, sodium lignosulfonate was precipitated by alcohol precipitation. After washing with alcohol and drying, glutathione-treated sodium lignosulfonate was obtained.

[0062] The mass ratio of sodium lignosulfonate, deionized water, EDC, NHS, and glutathione is 10:100:2:4:3.

[0063] (2) Preparation of acidifying agent by mixing

[0064] Sodium lignin sulfonate treated with glutathione is mixed with Brazilian tannin to obtain a mixed powder. The mixed powder is then mixed with deionized water to obtain a mixed solution. The mixed solution is then mixed with formic acid solution to obtain an acidifying agent.

[0065] The mass ratio of sodium lignin sulfonate treated with glutathione to Brazilian tannin is 1:1.

[0066] The mass ratio of the mixed powder to deionized water is 30:70;

[0067] The volume ratio of the mixed solution to the formic acid solution is 1:1;

[0068] The concentration of the formic acid solution is 85%.

[0069] Comparative Example 2

[0070] (1) Preparation of fumaric acid-treated sodium lignosulfonate

[0071] Sodium lignosulfonate was mixed with deionized water and stirred until completely dissolved. Then, tris(hydroxymethyl)aminomethane and fumaric acid were added. After the addition was completed, the pH was adjusted to 7.8. The temperature was then controlled at 42°C and stirred for 360 minutes. Sodium lignosulfonate was precipitated by alcohol precipitation, and then washed with alcohol and dried to obtain fumaric acid-treated sodium lignosulfonate.

[0072] The mass ratio of sodium lignosulfonate, deionized water, tris(hydroxymethyl)aminomethane, and fumaric acid is 10:80:3:2.

[0073] (2) Preparation of acidifying agent by mixing

[0074] Sodium lignosulfonate treated with fumaric acid is mixed with Brazilian tannin to obtain a mixed powder. The mixed powder is then mixed with deionized water to obtain a mixed solution. The mixed solution is then mixed with formic acid solution to obtain an emulsion, i.e., an acidifier.

[0075] The mass ratio of fumaric acid-treated sodium lignosulfonate to Brazilian tannin is 1:1.

[0076] The mass ratio of the mixed powder to deionized water is 30:70;

[0077] The volume ratio of the mixed solution to the formic acid solution is 1:1;

[0078] The concentration of the formic acid solution is 85%.

[0079] Example 4: Stability Test of Acidifier Emulsion

[0080] The stability of the acidifier emulsions in Examples 1-3 and Comparative Examples 1-2 was tested according to the method in GB / T1603-2001. 100 mL of acidifier emulsion was transferred to a clean and dry 100 mL graduated cylinder, which was placed in a constant temperature water bath at 30°C and allowed to stand for 1 hour. After 1 hour, the emulsion was removed and the separation was observed. The results are shown in Table 1.

[0081] Table 1

[0082]

[0083] Examples 1-3 involve special treatment of sodium lignosulfonate and its combination with tannins to prepare acidifying agents. The prepared acidifying agents have good stability and do not exhibit stratification or precipitation during stability tests.

[0084] Comparative Example 1 omitted the step of preparing fumaric acid-treated sodium lignosulfonate and directly treated the untreated sodium lignosulfonate with glutathione. The resulting acidifier had poor stability. In the stability test, no stratification occurred, but slight precipitation occurred.

[0085] Comparative Example 2 omitted the step of preparing glutathione-treated sodium lignosulfonate and directly mixed fumaric acid-treated sodium lignosulfonate to prepare the acidifier. The final acidifier had poor stability. In the stability test, no stratification occurred, but slight precipitation occurred.

[0086] Example 5: Effects of acidifiers on livestock irritation

[0087] The acidifier emulsions prepared in Examples 1-3 and Comparative Examples 1-2 were used to conduct palatability tests on domestic pigs. For each example and comparative example, 50 healthy domestic pigs weighing approximately 50 kg were selected and fed with feed containing the acidifier. The feeding method was to mix the feed with the emulsion. The mixed feed was given once in the morning and once in the evening. The amount of acidifier added was 0.5 wt% of the feed. The average daily feed intake on the day the mixed feed was consumed and the average daily feed intake from day 1 to day 5 after consuming the mixed feed were recorded. A control group was set up, which did not consume the mixed feed but only the unmixed ordinary feed. The results are shown in Table 2.

[0088] Table 2

[0089]

[0090] Examples 1-3 describe the preparation of acidifiers by specially treating sodium lignosulfonate and combining it with tannins. The acidifiers prepared and added to feed have low irritation to animals and can increase their feed intake to a certain extent.

[0091] Comparative Example 1 omits the step of preparing fumaric acid-treated sodium lignin sulfonate and directly treats the untreated sodium lignin sulfonate with glutathione. The resulting acidifier is added to the feed, which is somewhat irritating to the animals and reduces their feed intake.

[0092] Comparative Example 2 omitted the step of preparing glutathione-treated sodium lignin sulfonate and directly mixed fumaric acid-treated sodium lignin sulfonate to prepare the acidifier. The final acidifier was added to the feed, which was somewhat irritating to the animals and reduced their feed intake.

[0093] Example 6: Effect of acidifier on feed mold growth

[0094] The acidifying agents prepared in Examples 1-3 and Comparative Examples 1-2 were added to the feed at a dosage of 0.5 wt%. Then, according to the method of GB / T13092-2006, the mold growth of the feed after the addition of the acidifying agent was detected after different storage times. The total bacterial count of the feed was detected on the 1st, 10th, 20th, 30th and 50th days after the addition, in units of CFU / g. The results are shown in Table 3.

[0095] Excluding the acidifier, the feed formula is as follows: wheat bran 5.25%, corn 17.5%, barley 12.5%, fish meal 2%, cottonseed cake 3%, dried green vegetables 50%, green sugar 9%, salt 0.25%, and limestone powder 0.5%.

[0096] Table 3

[0097]

[0098] Examples 1-3 involve special treatment of sodium lignosulfonate and its combination with tannins to prepare an acidifier. When the prepared acidifier is added to feed, it can effectively prevent the feed from becoming moldy and maintain a low total bacterial count after long-term storage.

[0099] Comparative Example 1 omitted the step of preparing fumaric acid-treated sodium lignosulfonate and directly treated the untreated sodium lignosulfonate with glutathione. The resulting acidifier was added to the feed, which had a poor effect on preventing mold growth in the feed. After long-term storage, the total number of colonies was high.

[0100] Comparative Example 2 omitted the step of preparing glutathione-treated sodium lignosulfonate and directly mixed fumaric acid-treated sodium lignosulfonate to prepare the acidifier. The final acidifier was added to the feed, which had a poor effect on preventing mold growth and a high total bacterial count after long-term storage.

Claims

1. A method for preparing a low-irritant feed acidifier, characterized in that, The preparation method includes: Sodium lignosulfonate treated with fumaric acid: Sodium lignosulfonate was mixed with deionized water and stirred until completely dissolved. Then, tris(hydroxymethyl)aminomethane and fumaric acid were added. After the addition was completed, the pH was adjusted to 7.7-8.0 and stirred. Sodium lignosulfonate was precipitated by alcohol precipitation, and then washed with alcohol and dried to obtain fumaric acid-treated sodium lignosulfonate. The mass ratio of sodium lignosulfonate, deionized water, tris(hydroxymethyl)aminomethane, and fumaric acid is 9-11:75-85:2.5-3.5:1.7-2.

3. Glutathione-treated sodium lignin sulfonate: Sodium fumarate treated with lignin sulfonate was mixed with deionized water and stirred until completely dissolved. Then EDC and NHS were added, and the temperature was controlled by an ice-water bath while stirring. Glutathione was then added and stirred. After stirring, sodium lignin sulfonate was precipitated by alcohol precipitation, and then washed with alcohol and dried to obtain glutathione-treated sodium lignin sulfonate. The mass ratio of fumaric acid-treated sodium lignosulfonate, deionized water, EDC, NHS, and glutathione is 9-11:90-110:1.8-2.2:3.5-4.5:2.7-3.

3. Preparation of acidifying agents by mixing: The preparation method is as follows: glutathione-treated sodium lignosulfonate is mixed with Brazilian tannin to obtain a mixed powder, then the mixed powder is mixed with deionized water to obtain a mixed solution, and then the mixed solution is mixed with formic acid solution to obtain an acidifier; The mass ratio of sodium lignin sulfonate treated with glutathione to Brazilian tannin is 1:0.8-1.2; The mass ratio of the mixed powder to deionized water is 25-35:65-75; The volume ratio of the mixed solution to the formic acid solution is 1:0.8-1.

2.

2. The method for preparing a low-irritant feed acidifier according to claim 1, characterized in that: In the step of treating sodium lignosulfonate with fumaric acid, the stirring method is to control the temperature at 41-43℃ and stir for 320-390 minutes.

3. A method for preparing a low-irritant feed acidifier according to claim 1, characterized in that: In the step of treating sodium lignosulfonate with glutathione, the method of controlling the temperature and stirring using an ice-water bath is as follows: the temperature is controlled at 1-3℃ using an ice-water bath, and stirring is performed for 14-16 minutes.

4. A method for preparing a low-irritant feed acidifier according to claim 1, characterized in that: In the step of treating sodium lignosulfonate with glutathione, after adding glutathione, the stirring method is as follows: adjust the temperature to 51-55℃, control the stirring speed to 25-35r / min, and stir for 11.5-12.5h.

5. A method for preparing a low-irritant feed acidifier according to claim 1, characterized in that: In the step of preparing the acidifying agent, the concentration of the formic acid solution is 55-85%.

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