Preparation process of feed additive organic trace humic acid iron complex (chelate)

Abstract

The invention provides a preparation process of a feed additive organic trace humic acid iron (complex) chelate, the specific flow comprises coal (peat, lignite and weathered coal) mineral separation, coal mine crushing and oxidation chain scission, coal water slurry preparation, fine selection and impurity removal, biological acidification reaction, enzymatic hydrolysis reaction, chelation reaction and drying granulation, and the complex (complex) rate of the prepared complex (complex) is greater than 95%. The invention solves the technical problems that the existing humic acid iron product is prepared by physical modes such as mixing, roasting, washing, concentration crystallization and the like or chemical reaction and is low in utilization rate, and solves the technical problems that in the prior art, the pH value of gastrointestinal tracts is regulated only by utilizing acidity of ferric sulfate or humic acid is utilized to promote feed activation and absorption, regulate intestinal health and the like; and the problem that the iron absorption rate is improved by an iron combination form is not fundamentally solved.

Description

Technical Field

[0001] This application relates to the field of feed additive production technology, specifically to a preparation process of an organic trace humic acid iron complex (chelate) for feed additives. Background Technology

[0002] Iron is an essential macro-element for animal bodies, a component of hemoglobin and myoglobin, and plays a role in oxygen transport and storage. It is also a cofactor or active center for many enzymes, participating in various biochemical reactions and possessing multiple functions such as promoting animal growth and development, enhancing immunity, and resisting oxidative stress. Humic acid is widely found in nature, especially abundant in coal, and is used in agriculture, forestry, animal husbandry, fisheries, chemicals, petroleum, and other fields. Its hydroxyl and phenolic hydroxyl functional groups can efficiently chelate metal ions, enhancing the stability and biological activity of trace elements. It promotes feed absorption, increases hormone secretion, has antibacterial and anti-inflammatory effects, provides antioxidant protection, and enhances immunity, making it a natural organic carrier of trace elements. Humic acid trace elements align with the current calls and requirements for ecological agriculture, harmless agricultural production, and green environmental protection.

[0003] Currently, feed mills and livestock farms commonly use chemically synthesized inorganic iron as an iron source additive. However, it is prone to moisture absorption, has low absorption efficiency, and poor efficacy stability. While organic chelated iron is effective, it is expensive. Currently, there are humic acid-based iron products on the market, primarily functioning to adjust gastrointestinal pH using the acidity of ferric sulfate or to promote feed activation and absorption, and regulate intestinal health using humic acid. These products are manufactured using physical methods such as mixing, roasting, washing, concentration, crystallization, and pulverization, or through chemical reactions, resulting in low utilization rates and failing to fundamentally address the binding form of iron to improve its absorption rate. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a preparation process for organic trace humic acid iron (complex) chelates used as feed additives. This process solves the technical problems mentioned in the background section, where existing humic acid iron products are produced through physical methods such as mixing, roasting, washing, concentration, and crystallization, or through chemical reactions, resulting in low utilization rates. Furthermore, it addresses the issue that existing technologies merely utilize the acidity of ferric sulfate to adjust the pH value of the gastrointestinal tract or utilize humic acid to promote feed activation and absorption, and regulate intestinal health, without fundamentally addressing the issue of iron binding forms to improve iron absorption rates.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a preparation process for producing organic trace humic acid iron complexes (chelates) for feed additives, wherein, optionally, the preparation process for organic trace humic acid iron complexes (chelates) includes the following process steps: S1. Using multi-stage mineral processing equipment, peat, lignite, or weathered coal are subjected to three steps of screening, air separation, and magnetic separation to remove impurities, resulting in macromolecular chain humic acid.

[0006] S2. Mix the macromolecular chain humic acid and oxidant described in S1 at a mass ratio of 26-30:1-2, then pulverize them to a fineness of 100 mesh or higher using an electromagnetic ball mill, and further react them at 100-110°C for 2-3 hours to obtain medium-molecular chain humic acid.

[0007] S3. Add the medium-molecular-weight humic acid described in S2 into a high-speed stirred tank, add 40-50% of the total mass of the medium-molecular-weight humic acid to deionized water, stir at high speed with shear for 40-50 minutes, and then introduce ozone (unit: L / kg; standard conditions: 0℃, 101kPa) at 2-4 times the total mass of the medium-molecular-weight humic acid for further oxidation and chain breaking for 4-5 hours to obtain a small-molecular-weight humic acid slurry.

[0008] S4. Use a self-overflowing impurity removal device to refine and remove impurities from the small molecule chain humic acid slurry described in S3 to obtain high-purity humic acid raw slurry.

[0009] S5. Transfer the humic acid stock solution described in S4 into a reaction vessel, add an active glycoprotein and bacterial culture mixture at a mass ratio of 2-4:1-2 at a volume ratio of 5-8%, pressurize to 1.5-2 atmospheres, keep the temperature at 60-70℃ for 5-6 hours to obtain a highly active free humic acid stock solution.

[0010] S6. In the highly active free humic acid stock solution described in S5, add a mixture of active enzyme and sodium bicarbonate in a mass ratio of 1-3:2-6 at 3-5% by volume, pressurize the reaction vessel to 1-2 atmospheres, keep it at 55-65℃ for 6-8 hours to obtain a soluble humic acid stock solution.

[0011] S7. Mix the mixture of ferrous sulfate monohydrate and inhibitor in a mass ratio of 18-22:1-2 with the soluble humic acid stock solution described in S6 at a concentration of 700-800 g / L, and react at 80-90°C under normal pressure for 2-3 hours to obtain a mixture of small molecule humic acid complex (chelated) iron.

[0012] S8. The mixture of small molecule humic acid chelated iron described in S7 is centrifuged, filtered, impurity removed, dried, pulverized and granulated to obtain organic trace humic acid iron chelate.

[0013] Optionally, the humic acid may be derived from any one of peat, lignite, and weathered coal.

[0014] Optionally, the oxidant is chlorine dioxide.

[0015] Optionally, the active glycoprotein is yeast mannose protein. Optionally, the bacterial species is actinomycetes.

[0016] Optionally, the active enzyme is catalase.

[0017] Optionally, the inhibitor is citric acid.

[0018] The beneficial effects of this invention are as follows: 1. The organic trace humic acid iron complex (chelate) produced by the method of the present invention has the dual effects of iron and humic acid, and the complex (chelate) rate is greater than 95%.

[0019] 2. The iron absorption efficiency of the organic trace humic acid iron complex (chelate) produced by the method of the present invention is higher than that of inorganic iron.

[0020] 3. The organic trace humic acid iron complex (chelate) produced by the method of the present invention can prevent iron deficiency anemia in livestock and poultry and reduce the lignocellulosic content of broiler meat by 60.63%.

[0021] 4. The organic trace humic acid iron complex (chelate) produced by the method of the present invention is a green and efficient iron supplement suitable for common livestock and poultry. Attached Figure Description

[0022] Figure 1 The diagram shown is a schematic of the production process of the organic trace humic acid iron complex (chelate) of the present invention. Detailed Implementation

[0023] To make the objectives, steps, and advantages of the embodiments of the present invention clearer, the steps of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0024] The detection method used in this invention is as follows: Humic acid: determined by volumetric method or residual method (refer to GB / T 11957-2001 and NY / T 4120-2022).

[0025] Total iron: determined by atomic absorption spectrometry (refer to GB / T 13885-2017 Determination of iron content in feed).

[0026] Free iron: Atomic absorption spectrometry was used (free iron was first separated with methanol, and then the determination of iron content in feed was carried out in accordance with GB / T 13885-2017).

[0027] Moisture content: According to GB / T 6435-2014 "Determination of moisture content in feed".

[0028] Chelation rate calculation formula: Chelation rate (%) = (Total iron content - Free iron content) / Total iron content * 100%.

[0029] Please see Figure 1 The present invention provides a technical solution: a preparation process for producing organic trace humic acid iron complex (chelate) for feed additives, the specific process including coal (peat, lignite and weathered coal) beneficiation, coal crushing and oxidation chain breaking, coal-water slurry preparation, fine cleaning and impurity removal, biological acidification reaction, enzymatic hydrolysis reaction, chelation reaction and drying granulation.

[0030] Example 1 The preparation method of organic trace humic acid iron complex (chelate) includes the following process steps: S1. Using multi-stage mineral processing equipment, lignite is subjected to three steps of impurity removal: screening, air separation, and magnetic separation, to obtain macromolecular chain humic acid.

[0031] S2. Mix the macromolecular chain humic acid and chlorine dioxide described in S1 at a mass ratio of 28:1, then pulverize them to a fineness of 100 mesh or higher using an electromagnetic ball mill, and further react them at 110°C for 2.5 hours to obtain medium-molecular chain humic acid.

[0032] S3. The medium-molecular-chain humic acid described in S2 is added to a high-speed stirred tank, and deionized water is added at 43% of the total mass of the medium-molecular-chain humic acid. After high-speed shear stirring for 46 minutes, ozone (unit: L / kg; standard conditions: 0℃, 101kPa) with a volume of 3 times the total mass of the medium-molecular-chain humic acid is introduced for further oxidation and chain breaking for 4.2 hours to obtain a small-molecular-chain humic acid slurry.

[0033] S4. Use a self-overflowing impurity removal device to refine and remove impurities from the small molecule chain humic acid slurry described in S3 to obtain high-purity humic acid raw slurry.

[0034] S5. Transfer the humic acid stock solution described in S4 into a reaction vessel, add a mixture of yeast mannoprotein and actinomycetes at a mass ratio of 2:1 at 7% by volume, pressurize to 1.7 atmospheres, keep at 65°C for 5.4 hours to obtain a highly active free humic acid stock solution.

[0035] S6. In the highly active free humic acid stock solution described in S5, a mixture of catalase and sodium bicarbonate in a mass ratio of 1:3 is added at 4% by volume. The reaction vessel is pressurized to 1.7 atmospheres and kept at 60°C for 7 hours to obtain a soluble humic acid stock solution.

[0036] S7. A mixture of ferrous sulfate monohydrate and citric acid in a mass ratio of 20:1 is mixed with the soluble humic acid stock solution described in S6 at a concentration of 770 g / L. The mixture is then kept at 85°C under normal pressure for 2.5 hours to obtain a mixture of small molecule humic acid complexed (chelated) iron.

[0037] S8. The mixture of small molecule humic acid chelated iron described in S7 is centrifuged, filtered, impurity removed, dried, pulverized and granulated to obtain organic trace humic acid iron chelate.

[0038] Example 2 The preparation method of organic trace humic acid iron complex (chelate) includes the following process steps: S1. Using multi-stage mineral processing equipment, peat is purified through three steps: screening, air separation, and magnetic separation to obtain macromolecular chain humic acid.

[0039] S2. Mix the macromolecular chain humic acid and chlorine dioxide described in S1 at a mass ratio of 26:1.5, then pulverize them to a fineness of 100 mesh or higher using an electromagnetic ball mill, and further react them at 100°C for 3 hours to obtain medium-molecular chain humic acid.

[0040] S3. Add the medium-molecular-weight humic acid described in S2 into a high-speed stirred tank, add deionized water equal to 40% of the total mass of the medium-molecular-weight humic acid, stir at high speed with shear for 50 minutes, and then introduce ozone (unit: L / kg; standard conditions: 0℃, 101kPa) at twice the total mass of the medium-molecular-weight humic acid for further oxidation and chain breaking for 4 hours to obtain a small-molecular-weight humic acid slurry.

[0041] S4. Use a self-overflowing impurity removal device to refine and remove impurities from the small molecule chain humic acid slurry described in S3 to obtain high-purity humic acid raw slurry.

[0042] S5. Transfer the humic acid stock solution described in S4 into a reaction vessel, add 5% by volume of a mixture of yeast mannoprotein and actinomycetes at a mass ratio of 3:1.5, pressurize to 1.5 atmospheres, keep at 65°C for 5.4 hours to obtain a highly active free humic acid stock solution.

[0043] S6. In the highly active free humic acid stock solution described in S5, a mixture of catalase and sodium bicarbonate in a mass ratio of 1:2 is added at 3% by volume. The reaction vessel is pressurized to 1 atmosphere and kept at 60°C for 8 hours to obtain a soluble humic acid stock solution.

[0044] S7. A mixture of ferrous sulfate monohydrate and citric acid in a mass ratio of 20:1.5 is mixed with the soluble humic acid stock solution described in S6 at a concentration of 700 g / L. The mixture is then kept at 80°C under normal pressure for 3 hours to obtain a mixture of small molecule humic acid complex (chelated) iron.

[0045] S8. The mixture of small molecule humic acid chelated iron described in S7 is centrifuged, filtered, impurity removed, dried, pulverized and granulated to obtain organic trace humic acid iron chelate.

[0046] Example 3 The preparation method of organic trace humic acid iron complex (chelate) includes the following process steps: S1. Using multi-stage mineral processing equipment, weathered coal is subjected to three steps of impurity removal: screening, air separation, and magnetic separation, to obtain macromolecular chain humic acid.

[0047] S2. Mix the macromolecular chain humic acid and chlorine dioxide described in S1 at a mass ratio of 30:2, then pulverize them to a mesh size of 100 or higher using an electromagnetic ball mill, and further react them at 110°C for 2 hours to obtain medium-molecular chain humic acid.

[0048] S3. Add the medium-molecular-weight humic acid described in S2 into a high-speed stirred tank, add deionized water equal to 50% of the total mass of the medium-molecular-weight humic acid, stir at high speed with shear for 40 minutes, and then introduce ozone (unit: L / kg; standard conditions: 0℃, 101kPa) at 4 times the total mass of the medium-molecular-weight humic acid for further oxidation and chain breaking for 4.6 hours to obtain a small-molecular-weight humic acid slurry.

[0049] S4. Use a self-overflowing impurity removal device to refine and remove impurities from the small molecule chain humic acid slurry described in S3 to obtain high-purity humic acid raw slurry.

[0050] S5. Transfer the humic acid stock solution described in S4 into a reaction vessel, add 8% by volume a mixture of yeast mannoprotein and actinomycetes at a mass ratio of 4:2, pressurize to 2 atmospheres, keep warm at 60°C for 5 hours to obtain a highly active free humic acid stock solution.

[0051] S6. In the highly active free humic acid stock solution described in S5, a mixture of catalase and sodium bicarbonate in a mass ratio of 3:6 is added at 5% by volume. The reaction vessel is pressurized to 2 atmospheres and kept at 65°C for 8 hours to obtain a soluble humic acid stock solution.

[0052] S7. A mixture of ferrous sulfate monohydrate and citric acid in a mass ratio of 22:2 is mixed with the soluble humic acid stock solution described in S6 at a concentration of 800 g / L. The mixture is then kept at 90°C under normal pressure for 2 hours to obtain a mixture of small molecule humic acid complex (chelated) iron.

[0053] S8. The mixture of small molecule humic acid chelated iron described in S7 is centrifuged, filtered, impurity removed, dried, pulverized and granulated to obtain organic trace humic acid iron chelate.

[0054] Example 4 The preparation method of organic trace humic acid iron complex (chelate) includes the following process steps: S1. Using multi-stage mineral processing equipment, lignite is subjected to three steps of impurity removal: screening, air separation, and magnetic separation, to obtain macromolecular chain humic acid.

[0055] S2. Mix the macromolecular chain humic acid and chlorine dioxide described in S1 at a mass ratio of 27:1, then pulverize them to a fineness of 100 mesh or higher using an electromagnetic ball mill, and further react them at 100°C for 2.5 hours to obtain medium-molecular chain humic acid.

[0056] S3. Add the medium-molecular-weight humic acid described in S2 into a high-speed stirred tank, add deionized water at 46% of the total mass of the medium-molecular-weight humic acid, stir at high speed with shear for 43 minutes, and then introduce ozone (unit: L / kg; standard conditions: 0℃, 101kPa) at 2.8 times the total mass of the medium-molecular-weight humic acid for further oxidation and chain breaking for 5 hours to obtain a small-molecular-weight humic acid slurry.

[0057] S4. Use a self-overflowing impurity removal device to refine and remove impurities from the small molecule chain humic acid slurry described in S3 to obtain high-purity humic acid raw slurry.

[0058] S5. Transfer the humic acid stock solution described in S4 into a reaction vessel, add a mixture of yeast mannoprotein and actinomycetes at a mass ratio of 1.5:1 at 6% by volume, pressurize to 1.5 atmospheres, keep at 60°C for 6 hours to obtain a highly active free humic acid stock solution.

[0059] S6. In the highly active free humic acid stock solution described in S5, a mixture of catalase and sodium bicarbonate in a mass ratio of 2:5 is added at 4% by volume. The reaction vessel is pressurized to 2 atmospheres and kept at 60°C for 7 hours to obtain a soluble humic acid stock solution.

[0060] S7. A mixture of ferrous sulfate monohydrate and citric acid in a mass ratio of 18:1 is mixed with the soluble humic acid stock solution described in S6 at a concentration of 750 g / L. The mixture is then reacted at 85°C under normal pressure for 2.5 hours to obtain a mixture of small molecule humic acid complexed (chelated) iron.

[0061] S8. The mixture of small molecule humic acid chelated iron described in S7 is centrifuged, filtered, impurity removed, dried, pulverized and granulated to obtain organic trace humic acid iron chelate.

[0062] The technical indicators and quality requirements of the organic trace humic acid iron complexes prepared in Examples 1-4 are shown in Table 1.

[0063] The detection results of the organic trace humic acid iron complexes prepared in Examples 1-4 are shown in Table 1.

[0064] Table 1. Quality indicators and test results of the organic trace humic acid iron complexes (chelates) prepared in Examples 1-4

[0065] As shown in Table 1 above, the chelation rate of the organic trace humic acid iron complex is above 99%, which exceeds the standard of 95% required for most complexed iron on the market. It is an organic trace iron source supplement with a high chelation rate.

[0066] Example 1 Example 1 is an assessment of the effect of the organic trace humic acid iron complex (chelate) prepared in Example 1 on animal feeding.

[0067] 1. Experimental Materials and Methods Experimental materials: The organic trace humic acid iron complex (chelate) was the product produced in Example 1. Ferrous sulfate was purchased from Sichuan Jilongda Biotechnology Group Co., Ltd., with an iron content ≥20%.

[0068] Experimental animals and grouping: One-day-old broiler chickens were used, in a total of 4 sheds (sheds 1, 2, 3, and 4), with 23,000 chickens in each shed, for a total of 92,000 chickens. Sheds 1 and 2 were randomly assigned as control groups and fed a basal diet plus ferrous sulfate, while sheds 3 and 4 were assigned as experimental groups and fed a basal diet plus organic trace humic acid iron complex (chelate). The feeding amounts of ferrous sulfate from 1 to 21 days of age and organic trace humic acid iron complex (chelate) from 22 days of age to slaughter were 200 g / t and 300 g / t, respectively.

[0069] Experimental diets: The basal diets were formulated with reference to the nutritional requirements of broilers in the US NRC (1994). The composition and nutritional components of the diets are shown in Table 2.

[0070] Table 2. Basic diet and nutrient composition (dry matter basis) used in Example 1.

[0071]

[0072] The premix provides the following per kilogram of diet: Vitamin A 9,500 IU; Vitamin D 362.5 μg; Vitamin E 30 IU; Vitamin K 32.65 mg; Vitamin B1 2 mg; Vitamin B2 8 mg; Vitamin B6 3. ... 12 0.01 mg; Calcium pantothenate 12 mg; Niacin 35 mg; Folic acid 1.25 mg; Biotin 0.325 mg; Choline 1300 mg; Copper 8 mg; Zinc 85 mg; Manganese 80 mg; Selenium 0.25 mg; Iodine 0.7 mg. Crude protein, calcium, available phosphorus, and iron are measured values, and the rest are calculated values.

[0073] Feeding and Management: The experimental broiler chickens were raised in four-layer cages in greenhouses, each equipped with an automatic temperature control system. The temperature inside the greenhouses for 1-day-old broiler chickens was maintained at 34°C, then decreased by 1°C every two days until it was consistently maintained at 21°C. The relative humidity inside the greenhouses was maintained at 65%–70% during the first week, and decreased to 50%–65% and maintained thereafter during the second and third weeks. Incandescent lamps with a light intensity of 10–15 Ix were used in the greenhouses. During the first week, the light exposure was 23 hours followed by 1 hour of darkness; during the second to fourth weeks, the light exposure was 20 hours followed by 4 hours of darkness; subsequently, the light exposure was 23 hours followed by 1 hour of darkness until the end of the experiment; the lighting was uniform across each layer. The experimental broiler chickens had free access to feed and water via nipple drinkers, and daily management was carried out according to the requirements of a chicken farm.

[0074] Trial period: 42 days.

[0075] 2. Detection indicators Average daily feed intake (ADFI), average daily weight gain (ADG), feed conversion ratio (F / G), survival rate, woody meat, etc.

[0076] 3. Results Experimental data were initially processed using Excel (2013), and independent samples t-tests were performed using SPSS 17.0. Results are expressed as mean ± standard error.

[0077] The results of the production performance test are shown in Table 3. It can be seen that there was no significant difference in body weight, ADFI, and mortality rate at 42 days of age between diets supplemented with organic trace humic acid iron complex (chelate) and inorganic ferrous sulfate. P >0.05); the ADG level in the experimental group showed an increasing trend compared to the control group ( P <0.10), increased by 2.10 g / d; F / G showed a decreasing trend compared to the control group ( P <0.10), a decrease of 0.06.

[0078] Table 3. Effects of organic trace humic acid iron complex (chelate) on broiler production performance in Example 1

[0079] Note: Different capital letters in the superscript of peer data indicate extremely significant differences. P <0.01), different lowercase letters indicate significant differences ( P <0.05, no letter indicates no significant difference ( P >0.05), the same below.

[0080] The results of the woody meat trial are shown in Table 4. It can be seen that the proportion of woody meat in 21-day-old animals fed a diet supplemented with organic trace amounts of humic acid iron complex (chelate) was significantly lower than that of animals fed a diet supplemented with inorganic ferrous sulfate. P<0.05%, a decrease of 36.96%; the proportion of woody flesh in the 42-day-old experimental group was significantly lower than that in the control group ( P <0.01), a decrease of 60.63%.

[0081] Table 4. Effects of organic trace humic acid iron complex (chelate) on lignin in broiler chickens in Example 1.

[0082] As shown in Example 1, adding the organic trace humic acid iron complex (chelate) of the present invention to the basal diet has a tendency to increase the average daily weight gain of broilers and reduce the feed conversion ratio compared to ferrous sulfate, and significantly reduces the incidence of woody meat in broilers.

[0083] Example 2 Example 2 is an assessment of the effect of the organic trace humic acid iron complex (chelate) prepared in Example 1 on animal feeding.

[0084] 1. Materials and Methods Experimental materials: The organic trace humic acid iron complex (chelate) was the product produced in Example 1; ferrous sulfate was purchased from Sichuan Jilongda Biotechnology Group Co., Ltd., with an iron content ≥20%; sodium humate was provided by Shandong Asia-Pacific Haihua Biotechnology Co., Ltd.

[0085] Experimental animals and grouping: 120 healthy 70-day-old Duroc × Landrace × Large White crossbred growing pigs weighing approximately 27.34 kg were selected and randomly divided into 4 groups, with 6 replicates per group and 5 pigs per replicate. The control group (Group I) was fed a basal diet supplemented with a mixture of sodium humate and ferrous sulfate (50 g sodium humate + 300 g ferrous sulfate) at a dose of 350 g / t. The experimental groups (Groups II, III, and IV) were fed a basal diet supplemented with 150 g / t, 250 g / t, and 350 g / t humate-iron complex (chelate), respectively.

[0086] Experimental diet: The base diet was the pig farm's self-prepared diet. The formula and nutritional components are shown in Table 5.

[0087] Table 5. Basic diet formulation and nutrient composition (dry matter basis) used in Example 2.

[0088] Note: The premix contains trace elements and vitamin additives; except for metabolizable energy, all other values ​​are measured values.

[0089] Feeding and management: The experimental pigs were fed twice a day, once in the morning and once in the afternoon, and had free access to food and water. Daily management and disease prevention were carried out in accordance with the requirements of the pig farm.

[0090] Experimental period: The entire experimental period was 40 days, including a 5-day pre-feeding period.

[0091] 2. Detection indicators 2.1 Growth performance: Fasted individuals were weighed at 8:00 AM on day 0 and day 35 of the experiment. Feed consumption was recorded in replicates, and the average daily weight gain, average daily feed intake, and feed conversion ratio were calculated.

[0092] 2.2 Skin color measurement: On days 14 and 35 of the experiment, two round pieces of pig hair with a diameter of about 8 cm were cut off from the shoulder and upper rump of the pigs respectively. A 100-watt incandescent lamp was placed 1.5 m above the cement floor of the pen, and the redness "a" value and yellowness "b" value of the skin were measured using a TC-PIA fully automatic colorimeter.

[0093] 3. Results Experimental data were statistically analyzed using Excel (2007), and SPSS 23 was used for analysis of variance and Duncan's multiple comparisons. Results are expressed as mean ± standard error.

[0094] The results of the growth performance test are shown in Table 6. It can be seen that the average daily weight gain of group III was significantly higher than that of group I. P <0.05); the material weight ratios of groups IV and III were significantly lower than those of group I ( P <0.05); Group III showed an increase of 10.5% in average daily weight gain and 8.1% in feed conversion ratio compared to Group I.

[0095] Table 6. Effects of organic trace amounts of humic acid iron complex (chelate) on the growth performance of growing pigs in Example 2.

[0096] The results of the skin color test are shown in Table 7. It can be seen that the a value of group III on day 35 was significantly higher than that of group I. P< The a value of the remaining experimental groups was 0.05, and the a values ​​of the remaining experimental groups were higher than those of Group I on days 14 and 35. This indicates that humic acid iron complex (chelate) can increase the redness of the skin of growing pigs.

[0097] Table 7. Effects of organic trace amounts of humic acid iron complex (chelate) on skin color of growing pigs in Example 2.

[0098] As shown in Example 2, adding the organic trace humic acid iron complex (chelate) of the present invention to the basal diet can significantly increase the average daily weight gain of growing pigs, reduce the feed conversion ratio, and improve skin redness compared to simply adding sodium humate and ferrous sulfate.

[0099] As can be seen from Example 1 and Example 2, organic trace humic acid chelated iron, compared to single inorganic iron and mixtures of inorganic iron and sodium humate, exhibits growth-promoting and meat-quality-improving effects. This is presumably related to the increased absorption rate of chelated iron ions due to humic acid and the activating and antibacterial / anti-inflammatory properties of humic acid in feed. Therefore, organic trace humic acid iron chelate is a green and efficient organic iron supplement with broad application prospects.

Claims

1. A preparation process for an organic trace humic acid iron complex (chelate) compound used as a feed additive, characterized in that, It includes the following steps: S1. Using multi-stage mineral processing equipment, peat, lignite, or weathered coal are purified in three steps: screening, air separation, and magnetic separation to obtain macromolecular chain humic acid. S2. Mix the macromolecular chain humic acid and oxidant described in S1 at a mass ratio of 26-30:1-2, then pulverize them to a fineness of 100 mesh or higher using an electromagnetic ball mill, and further react them at 100-110°C for 2-3 hours to obtain medium-molecular chain humic acid. S3. Add the medium molecular chain humic acid described in S2 into a high-speed stirred tank, add 40-50% of the total mass of the medium molecular chain humic acid to deionized water, stir at high speed and shear for 40-50 minutes, then introduce ozone at 2-4 times the total mass of the medium molecular chain humic acid to further oxidize and break the chain for 4-5 hours to obtain a small molecular chain humic acid slurry. S4. Use a self-overflowing impurity removal device to select and remove impurities from the small molecule chain humic acid slurry described in S3 to obtain high-purity humic acid raw slurry; S5. Transfer the humic acid stock solution described in S4 into a reaction vessel, add an active glycoprotein and bacterial culture mixture at a mass ratio of 2-4:1-2 at a volume ratio of 5-8%, pressurize to 1.5-2 atmospheres, keep warm at 60-70℃ for 5-6 hours to obtain a highly active free humic acid stock solution. S6. In the highly active free humic acid stock solution described in S5, add a mixture of active enzyme and sodium bicarbonate in a mass ratio of 1-3:2-6 at 3-5% by volume, pressurize the reaction vessel to 1-2 atmospheres, keep it at 55-65℃ for 6-8 hours to obtain a soluble humic acid stock solution. S7. Mix the mixture of ferrous sulfate monohydrate and inhibitor in a mass ratio of 18-22:1-2 with the soluble humic acid stock solution described in S6 at a concentration of 700-800 g / L, and keep the mixture at 80-90°C under normal pressure for 2-3 hours to obtain a mixture of small molecule humic acid complex (chelated) iron. S8. The mixture of small molecule humic acid chelated iron described in S7 is centrifuged, filtered, impurity removed, dried, pulverized and granulated to obtain organic trace humic acid iron chelate.

2. The preparation process of the feed additive organic trace humic acid iron complex (chelate) according to claim 1, characterized in that, The oxidant is chlorine dioxide.

3. The preparation process of the feed additive organic trace humic acid iron complex (chelate) according to claim 1, characterized in that, The active glycoprotein is yeast mannoprotein.

4. The preparation process of the feed additive organic trace humic acid iron complex (chelate) according to claim 1, characterized in that, The bacterial species is actinomycetes.

5. The preparation process of an organic trace humic acid iron complex (chelate) for feed additives according to claim 1, characterized in that, The active enzyme is catalase.

6. The preparation process of an organic trace humic acid iron complex (chelate) for feed additives according to claim 1, characterized in that, The inhibitor is citric acid.

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