阅读说明：本技术 一种低金属残留防结块蜂胶粉的制备方法 (Preparation method of low-metal-residue anti-caking propolis powder ) 是由 龙卫平 于 2020-04-17 设计创作，主要内容包括：本发明公开了一种低金属残留防结块蜂胶粉的制备方法,属于蜂胶类产品制备技术领域。本发明用聚乙烯亚胺水溶液作为硅胶的浸渗液,作为螯合材料对金属离子能产生很强的螯合作用,能够高效吸附重金属离子,并且羧基化纤维素在重金属的催化作用下与乙醇发生酯化,吸收重金属离子后容易与蜂胶粉分离,因而本发明的蜂胶粉的重金属残留量较低；抗结剂由微晶纤维素和纳米二氧化钛组成,微晶纤维素不仅通过吸湿表现出良好的抗结性能,还能在冷冻保存状态下防止有水分冷冻结块,纳米二氧化钛对蜂胶粉中黄酮类物质起到防氧化作用,提高蜂胶粉中黄酮含量,另外它还具有良好的导电性能,减少蜂胶粉内部静电,从而避免蜂胶粉结块。(The invention discloses a preparation method of low-metal-residue anti-caking propolis powder, belonging to the technical field of propolis product preparation. The invention uses the polyethyleneimine water solution as the infiltration solution of the silica gel, and the polyethyleneimine water solution as the chelating material can generate strong chelating action on metal ions, can efficiently adsorb heavy metal ions, and the carboxylated cellulose is esterified with ethanol under the catalytic action of heavy metal, and is easy to separate from the propolis powder after absorbing the heavy metal ions, so the propolis powder has low heavy metal residue; the anticaking agent consists of microcrystalline cellulose and nano titanium dioxide, the microcrystalline cellulose not only shows good anticaking performance through moisture absorption, but also can prevent water from freezing and caking in a frozen storage state, the nano titanium dioxide plays an anti-oxidation role on flavonoid substances in the propolis powder, the flavone content in the propolis powder is improved, in addition, the nano titanium dioxide also has good electric conductivity, and the internal static electricity of the propolis powder is reduced, so that the propolis powder is prevented from caking.)

1. A preparation method of low-metal residue anti-caking propolis powder is characterized by comprising the following specific preparation steps:

(1) dispersing and softening natural propolis with an ethanol aqueous solution, adding a cellulose adsorbent to prepare a propolis suspension, placing nano silica gel in a polyethyleneimine aqueous solution with the mass fraction of 25%, soaking for 10-12 min, filtering to remove filtrate, air-drying, placing on a filter hole of a suction filter funnel, adding the prepared propolis suspension, carrying out suction filtration, repeatedly flushing the filter hole with absolute ethyl alcohol, taking the lower liquid, and carrying out suction filtration for 3-4 times to obtain a metal-removed propolis immersion liquid;

(2) placing the above metal-removed propolis steep in a freezing chamber, and freezing to obtain frozen propolis block;

(3) putting the obtained frozen propolis blocks into a grinding and crushing machine, crushing the frozen propolis blocks into propolis blocks with 50-100 meshes, then sending the propolis blocks into a jet mill, carrying out secondary crushing, carrying out circular crushing, screening out powder particles with the particle size of less than 400 meshes to obtain propolis powder, mixing the propolis powder with an anticaking agent, and stirring and dispersing the mixture by a dry powder stirrer at the rotating speed of 300-500 r/min for 40-50 min to obtain low-metal-residue anticaking propolis powder;

the cellulose adsorbent is prepared by the following specific steps:

(1) dispersing nano cellulose in deionized water in a reaction kettle, adding sodium bromide and tetramethyl piperidine, stirring for 20-30 min, adding a sodium hypochlorite solution with the mass fraction of 10% into the reaction kettle, adjusting the pH to 9.0-10.0, and reacting for 3-5 h to prepare carboxylated cellulose;

(2) mixing 30-35 parts by weight of the carboxylated cellulose, 50-60 parts by weight of hydrogen peroxide with the mass fraction of 20%, 70-80 parts by weight of deionized water and 10-15 parts by weight of waste tea powder, stirring and dispersing to obtain a mixed glue solution, collecting the obtained lower-layer precipitate, washing the precipitate with deionized water for 3-5 times, and drying to obtain the cellulose adsorbent.

2. The preparation method of the low-metal residue anti-caking propolis powder as claimed in claim 1, which is characterized in that:

the ethanol water solution used in the specific preparation step (1) of the low-metal residue anti-caking propolis powder is 5 times of the mass of natural propolis, and the cellulose adsorbent accounts for 5% of the mass of the natural propolis.

3. The preparation method of the low-metal residue anti-caking propolis powder as claimed in claim 1, which is characterized in that: the mass fraction of the ethanol aqueous solution used in the specific preparation step (1) of the low-metal residue anti-caking propolis powder is preferably 50%.

4. The preparation method of the low-metal residue anti-caking propolis powder as claimed in claim 1, which is characterized in that: the cold-working process in the specific preparation step (2) of the low-metal residue anti-caking propolis powder is as follows: firstly, adjusting the temperature of a freezing chamber to-8 to-12 ℃, freezing for 10-15 min, then cooling to-15 to-20 ℃, freezing for 5-10 min, then adjusting the temperature of the freezing chamber to-25 to-20 ℃, and freezing for 5-10 min.

5. The preparation method of the low-metal residue anti-caking propolis powder as claimed in claim 1, which is characterized in that: the low-metal residue anti-caking propolis powder is prepared by pre-dehumidifying a freezing chamber before freezing in the step (2) to control the humidity to be 10-15% RH.

6. The preparation method of the low-metal residue anti-caking propolis powder as claimed in claim 1, which is characterized in that:

the specific preparation step (3) of the low-metal residue anti-caking propolis powder comprises mixing the propolis powder and an anti-caking agent at a mass ratio of 30: 1.

7. The preparation method of the low-metal residue anti-caking propolis powder as claimed in claim 1, which is characterized in that: the anti-caking agent in the specific preparation step (3) of the low-metal residue anti-caking propolis powder is prepared by uniformly mixing microcrystalline cellulose of 400 meshes and nano titanium dioxide of 400 meshes according to the mass ratio of 2: 1.

8. The preparation method of the low-metal residue anti-caking propolis powder as claimed in claim 1, which is characterized in that: the cellulose adsorbent is prepared from the raw materials in the step (1) in parts by weight, and comprises 30-35 parts of nano cellulose, 300-350 parts of deionized water, 1-2 parts of sodium bromide, 4-5 parts of tetramethylpiperidine and 50-60 parts of a sodium hypochlorite solution with the mass fraction of 10%.

9. The preparation method of the low-metal residue anti-caking propolis powder as claimed in claim 1, which is characterized in that: the cellulose adsorbent is prepared by using ammonia water with the mass fraction of 20% when the pH is adjusted in the specific preparation step (1).

Technical Field

The invention discloses a preparation method of low-metal-residue anti-caking propolis powder, belonging to the technical field of propolis product preparation.

Background

Propolis powder is a powdery propolis product as the name implies, and is a propolis product prepared by extracting pure propolis (98%) from raw propolis at a low temperature, then crushing at a low temperature, and adding edible and medical raw and auxiliary materials. Propolis is yellowish brown, dark brown or greenish, and slightly bitter. The main components of the propolis liquid mainly comprise 55% of resin and balm, 30% of beeswax, 10% of aromatic volatile oil and 5% of pollen impurities, and chemists separate more than 300 components such as flavone, mushroom alkene, organic acid, aromatic aldehyde, alcohol, lipid, polysaccharide, amino acid, vitamin, enzyme, mineral substances and the like from propolis, so that the propolis liquid is widely regarded by the medical and health fields. The propolis powder is prepared by hot air drying wax-free purified propolis fluid extract by modern process, pulverizing dried propolis blocks, sieving, and adding superfine silicon dioxide as anti-coagulating agent into propolis. Propolis is insoluble in water, and most of its effective components are soluble in ethanol. The prepared propolis extract has viscosity, becomes brittle when the temperature is lower than 15 ℃, and is easy to crush; softening at 36 deg.C, and forming viscous liquid at 65 deg.C, so that the propolis extract is difficult to dry by conventional drying process such as hot air drying and vacuum drying, and is time-consuming and energy-consuming, and the prepared propolis dry extract is difficult to pulverize into powder due to easy heating and viscosity change by conventional pulverizer.

The propolis powder contains no wax and silicon dioxide, has good dispersion, no coagulation, easy storage and transportation, and is one of the most ideal products for food, medicine and daily chemical enterprises at present. Food: at present, the health food industry is rising, the efficacy of the propolis powder is widely known, so a series of health foods such as propolis tablets, propolis capsules, propolis liquid, propolis tincture and the like with the content of 30% -90% are used. Medicine: the pharmacology of propolis is well known, so that the propolis has good effects on improving immunity, preventing tumors, resisting oxidation, protecting liver, reducing blood fat, reducing blood sugar, resisting bacteria and inflammation, resisting viruses, various skin diseases, digestive and urinary system diseases, bronchitis, tumors, oral ulcer and the like. Daily chemical: effective substances in propolis, such as flavonoids, flavonols, terpenes, enzymes, various vitamins, polyphenols, polysaccharides, resins, organic acids and the like, are widely applied to the fields of antibacterial and anti-inflammatory toothpaste, antibacterial soap, cosmetics and the like.

The production process of propolis powder at present is mostly to extract crude propolis with ethanol, remove beeswax and lead, recover and remove ethanol completely, freeze-dry to obtain propolis dry extract, pulverize at low temperature into propolis powder, and add suitable auxiliary materials to prepare the propolis powder. The production by adopting the process usually needs to be added with expensive freeze drying and low-temperature crushing equipment, thereby greatly increasing the production cost. The storage condition of the produced propolis powder is required to be controlled below 20 ℃, otherwise the propolis powder is easy to agglomerate and is not easy to be prepared into solid preparations such as propolis capsules, tablets and the like, thereby limiting the application range of the propolis.

Due to the imperfect production process, the large number of propolis products in the market have the defect of imperfect quality, such as incomplete impurity removal, unscientific deleading method, insufficiently fine filtration, incomplete removal of some soluble inactive substances, ineffective removal of a sensitization source, incomplete extraction process, influence of inappropriate parameters on the total flavone content of the final product and the like, so that the finally prepared propolis has potential quality safety hazards, such as: low purity, excessive heavy metal residue, low total flavone content, etc. The health care and adjuvant treatment effects of propolis are greatly reduced.

Therefore, the invention of the propolis powder with high total flavone content, low heavy metal residue and difficult caking is necessary for the technical field of propolis product preparation.

Disclosure of Invention

The invention mainly solves the technical problems, and provides a preparation method of low-metal-residue anti-caking propolis powder aiming at the defects that the total flavone content of a propolis product is low, the heavy metal residue exceeds the standard and the propolis powder is easy to cake in a storage state due to the imperfect production or extraction process of the propolis powder at present.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the preparation method of the low-metal residue anti-caking propolis powder comprises the following steps:

(1) dispersing and softening natural propolis with an ethanol aqueous solution, adding a cellulose adsorbent to prepare a propolis suspension, placing nano silica gel in a polyethyleneimine aqueous solution with the mass fraction of 25%, soaking for 10-12 min, filtering to remove filtrate, air-drying, placing on a filter hole of a suction filter funnel, adding the prepared propolis suspension, carrying out suction filtration, repeatedly flushing the filter hole with absolute ethyl alcohol, taking the lower liquid, and carrying out suction filtration for 3-4 times to obtain a metal-removed propolis immersion liquid;

(2) placing the above metal-removed propolis steep in a freezing chamber, and freezing to obtain frozen propolis block;

(3) putting the obtained frozen propolis blocks into a grinding and crushing machine, crushing the frozen propolis blocks into propolis blocks with 50-100 meshes, then sending the propolis blocks into a jet mill, carrying out secondary crushing, carrying out circular crushing, screening out powder particles with the particle size of less than 400 meshes to obtain propolis powder, mixing the propolis powder with an anticaking agent, and stirring and dispersing the mixture by a dry powder stirrer at the rotating speed of 300-500 r/min for 40-50 min to obtain low-metal-residue anticaking propolis powder;

the cellulose adsorbent is prepared by the following specific steps:

(1) dispersing nano cellulose in deionized water in a reaction kettle, adding sodium bromide and tetramethyl piperidine, stirring for 20-30 min, adding a sodium hypochlorite solution with the mass fraction of 10% into the reaction kettle, adjusting the pH to 9.0-10.0, and reacting for 3-5 h to prepare carboxylated cellulose;

(2) mixing 30-35 parts by weight of the carboxylated cellulose, 50-60 parts by weight of hydrogen peroxide with the mass fraction of 20%, 70-80 parts by weight of deionized water and 10-15 parts by weight of waste tea powder, stirring and dispersing to obtain a mixed glue solution, collecting the obtained lower-layer precipitate, washing the precipitate with deionized water for 3-5 times, and drying to obtain the cellulose adsorbent.

The ethanol water solution used in the specific preparation step (1) of the low-metal residue anti-caking propolis powder is 5 times of the mass of natural propolis, and the cellulose adsorbent accounts for 5% of the mass of the natural propolis.

The mass fraction of the ethanol aqueous solution used in the specific preparation step (1) of the low-metal residue anti-caking propolis powder is preferably 50%.

The cold-working process in the specific preparation step (2) of the low-metal residue anti-caking propolis powder is as follows: firstly, adjusting the temperature of a freezing chamber to-8 to-12 ℃, freezing for 10-15 min, then cooling to-15 to-20 ℃, freezing for 5-10 min, then adjusting the temperature of the freezing chamber to-25 to-20 ℃, and freezing for 5-10 min.

The low-metal residue anti-caking propolis powder is prepared by pre-dehumidifying a freezing chamber before freezing in the step (2) to control the humidity to be 10-15% RH.

The specific preparation step (3) of the low-metal residue anti-caking propolis powder comprises mixing the propolis powder and an anti-caking agent at a mass ratio of 30: 1.

The anti-caking agent in the specific preparation step (3) of the low-metal residue anti-caking propolis powder is prepared by uniformly mixing microcrystalline cellulose of 400 meshes and nano titanium dioxide of 400 meshes according to the mass ratio of 2: 1.

The cellulose adsorbent is prepared from the raw materials in the step (1) in parts by weight, and comprises 30-35 parts of nano cellulose, 300-350 parts of deionized water, 1-2 parts of sodium bromide, 4-5 parts of tetramethylpiperidine and 50-60 parts of a sodium hypochlorite solution with the mass fraction of 10%.

The cellulose adsorbent is prepared by using ammonia water with the mass fraction of 20% when the pH is adjusted in the specific preparation step (1).

The invention has the beneficial effects that:

(1) the invention uses the polyethyleneimine water solution as the infiltration solution of the silica gel, because the polyethyleneimine is a water-soluble polyamine, the linear macromolecular chain has a large amount of amino atoms, the polyethyleneimine is tightly adsorbed on the inner surface of the pores of the silica gel after the impregnation of the nano silica gel, and can generate strong chelation to metal ions as a chelating material, while the cellulose adsorbent is coated on the surface of the chelating adsorption material to form a nano filter membrane, in the process of preparing the cellulose adsorbent, tetramethyl pyridine is used for oxidizing hydroxymethyl on the surface of the nano cellulose to form carboxyl, so that the surface of the nano cellulose is rough and rich in pores, the carboxyl group on the surface can be ionized into hydrogen ions in water to be acidic, the negative electric group after the dissociation is a hydrocarbon group, can be adsorbed and combined with other heavy metal cations in the solution, can rapidly enter the material to be adsorbed and concentrated, and can efficiently adsorb the heavy metal ions, the carboxylated cellulose is esterified with ethanol under the catalytic action of heavy metal, and is easy to separate from the propolis powder after absorbing heavy metal ions, so that the heavy metal residual quantity of the propolis powder is low;

(2) the invention removes metal from natural propolis, freezes, crushes and screens, then add anticaking agent to mix, get low metal residue anticaking propolis powder, wherein anticaking agent is made up of microcrystalline cellulose and nanometer titanium dioxide, propolis extract adopts jet milling to crush and screen, can circulate, and crush effectually, mix with anticaking agent with identical graininess to form highly dispersed, powder with good fluidity evenly, microcrystalline cellulose not only shows good anticaking performance through absorbing moisture, can also prevent water from freezing and agglomerating under the state of freezing preservation, this is because microcrystalline cellulose can inhibit the ice crystal from growing up, thus facilitate the access and use of propolis powder, need not wait for the temperature change can use propolis powder, the service temperature range of the expanded propolis powder, and nanometer titanium dioxide plays an anti-oxidation role to flavonoid in propolis powder, improve the content of flavone in propolis powder, in addition, the conductive propolis powder has good conductivity, reduces static inside the propolis powder, thereby avoiding the agglomeration of the propolis powder and having wide application prospect.

Detailed Description

Dispersing 30-35 parts of nano cellulose in 300-350 parts of deionized water in a reaction kettle, adding 1-2 parts of sodium bromide and 4-5 parts of tetramethyl piperidine, stirring for 20-30 min, adding 50-60 parts of a 10% sodium hypochlorite solution in the reaction kettle, adjusting the pH to 9.0-10.0 by using 20% ammonia water in mass fraction, and reacting for 3-5 h to prepare carboxylated cellulose; mixing 30-35 parts by weight of the carboxylated cellulose, 50-60 parts by weight of 20% hydrogen peroxide, 70-80 parts by weight of deionized water and 10-15 parts by weight of waste tea powder, stirring and dispersing to obtain a mixed glue solution, collecting the obtained lower-layer precipitate, washing the precipitate with deionized water for 3-5 times, and drying to obtain a cellulose adsorbent; dispersing and softening natural propolis by using an ethanol aqueous solution with the mass fraction of 50% which is 5 times of the mass of the natural propolis, adding the cellulose adsorbent accounting for 5% of the mass of the natural propolis to prepare a propolis suspension, placing nano silica gel in a polyethyleneimine aqueous solution with the mass fraction of 25%, soaking for 10-12 min, filtering to remove filtrate, air-drying, placing on a filter hole of a suction filter funnel, adding the prepared propolis suspension, carrying out suction filtration, repeatedly flushing the filter hole by using absolute ethyl alcohol, taking the lower liquid, and carrying out suction filtration for 3-4 times to obtain a metal-removed propolis immersion liquid; placing the metal-removed propolis immersion liquid into a freezing chamber, freezing for 10-15 min by adjusting the temperature of the freezing chamber to-8 to-12 ℃, then cooling to-15 to-20 ℃, freezing for 5-10 min, then adjusting the temperature of the freezing chamber to-25 to-20 ℃, freezing for 5-10 min to obtain a frozen propolis block, and dehumidifying the freezing chamber in advance before freezing to control the humidity to be 10-15% RH; and (2) putting the frozen propolis blocks into a grinding crusher, crushing the frozen propolis blocks into 50-100 meshes of propolis blocks, then sending the propolis blocks into an airflow crusher, carrying out secondary crushing, carrying out circulating crushing, screening out powder particles with the particle size of less than 400 meshes to obtain propolis powder, mixing the propolis powder and an anticaking agent according to the mass ratio of 30: 1, stirring and dispersing the mixture for 40-50 min at the rotating speed of 300-500 r/min by using a dry powder stirrer to obtain the low-metal residual anticaking propolis powder, wherein the anticaking agent is formed by uniformly mixing 400-mesh microcrystalline cellulose and 400-mesh nano titanium dioxide according to the mass ratio of 2: 1.