CN111838680A - Production method of high-absorption nano calcium, product and application thereof - Google Patents

Production method of high-absorption nano calcium, product and application thereof Download PDF

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CN111838680A
CN111838680A CN202010516426.8A CN202010516426A CN111838680A CN 111838680 A CN111838680 A CN 111838680A CN 202010516426 A CN202010516426 A CN 202010516426A CN 111838680 A CN111838680 A CN 111838680A
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calcium
nano
eggshells
nano calcium
organic acid
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沈方雄
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Quality Every China Co ltd
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Quality Every China Co ltd
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/16Inorganic salts, minerals or trace elements
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/03Organic compounds
    • A23L29/05Organic compounds containing phosphorus as heteroatom
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs

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Abstract

The invention discloses a production method of high-absorption nano calcium, which comprises the following steps: step one, washing eggshells with water, alkali liquor and water in sequence, then respectively baking the eggshells at 55-60 ℃, 90-100 ℃, 170-180 ℃, 90-100 ℃ and 45-50 ℃ in sequence, spraying organic acid on the surfaces of the eggshells every 20-30 s in the drying process of 5 temperatures, then crushing the baked eggshells to obtain eggshell powder, adding the eggshells into the eggshells for soaking, and then filtering and collecting a calcium-containing acid solution; and step two, adding absolute ethyl alcohol into the calcium-containing acid solution, stirring, centrifuging, taking the solid, washing the solid by adopting the absolute ethyl alcohol, and then freeze-drying to obtain the nano calcium. The invention has the advantages of simple preparation process, small particle size of the prepared nano calcium, high solubility and easy absorption. The invention provides nano calcium and food containing the same, and also provides application of the nano calcium in preparation of products for increasing bone mineral density.

Description

Production method of high-absorption nano calcium, product and application thereof
Technical Field
The invention relates to the field of eggshell deep processing. More particularly, the invention relates to a production method of high-absorption nano calcium, a product and application thereof.
Background
The eggshell accounts for 10-12% of the weight of the whole egg and consists of an upper shell membrane, a lower shell membrane and an eggshell, wherein the eggshell is a calcareous hard shell and is positioned between the upper shell membrane and the lower shell membrane. The surface of the eggshell is provided with a large number of absorption holes, and each eggshell is provided with about ten thousand small holes, which is beneficial to forming fine and powdery powder. The eggshell contains 95% mineral, 3.3% protein, 1% water, 0.03% fat, and the balance carbohydrate and other organic substances. The mineral component of the eggshell is mainly calcium carbonate accounting for about 94 percent, and the rest is magnesium carbonate and calcium phosphate, wherein the content of calcium and phosphorus respectively accounts for 34.9 percent and 0.2 percent of the dry substance of the eggshell. In recent years, calcium supplements have been developed rapidly, such as calcium carbonate, which contains relatively high amounts of calcium and is most widely used in this class of calcium preparation because of its safety, efficacy and, in particular, low cost, but calcium carbonate is basic and has low solubility and must be absorbed after reacting with a large amount of gastric acid in the stomach to form ionized calcium. For example, calcium oxide has high calcium content and best water solubility, and has been used for supplementing calcium in emergency, but is basically eliminated at present because of large side effects such as acute toxicity and the like. Such as calcium lactate, calcium acetate, calcium gluconate and calcium citrate, which are organic calcium sources and have relatively low calcium content, but high absorption rate, no influence on gastric acid secretion and no acute toxicity. The calcium source of the eggshell is mainly calcium carbonate which is not easy to absorb, so how to process the calcium in the eggshell into the calcium source product which is easy to absorb is worth thinking.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
The invention also aims to provide a production method of the high-absorption nano calcium, which has simple preparation process, small particle size of the prepared nano calcium, high solubility and easy absorption.
Provides a nanometer calcium, the particle size of the nanometer calcium is less than 1000nm, the calcium content is more than 15 percent, and the solubility in water is high.
Provides food containing nano calcium, and food ingredients or additives or nutritional functional food or health food containing nano calcium.
Provides an application of nano calcium in preparing products for increasing bone mineral density, and has excellent effect of increasing bone mineral density.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for producing high absorption nano calcium, comprising the steps of:
step one, cleaning eggshells with water, alkali liquor and water in sequence, then baking the eggshells at 55-60 ℃, 90-100 ℃, 170-180 ℃, 90-100 ℃ and 45-50 ℃ for 3-5 min, 8-10 min, 3-5 min and 3-5 min respectively, spraying organic acid on the surfaces of the eggshells every 20-30 s in the drying process of 5 temperatures, then crushing the baked eggshells to obtain eggshell powder, adding organic acid with the mass 1-2 times of that of the eggshell powder into the eggshell powder, soaking the eggshell powder for 2-3 h, 4-5 h, 18-20 h, 15-18 h and 4-5 h at the temperature of 20-25 ℃, 38-42 ℃, 60-65 ℃, 80-90 ℃ and 38-42 ℃ in sequence, and then filtering and collecting an acid solution containing calcium;
Wherein the alkali liquor is a sodium bicarbonate water solution with the mass fraction of 3-5%, the particle size of the eggshell powder is smaller than 100 meshes, the organic acid for spraying and the organic acid for soaking are the same in type, and the amount of the organic acid is 0.3-0.5% of the eggshell mass each time the organic acid is sprayed;
and secondly, adding absolute ethyl alcohol into the calcium-containing acid solution according to the mass ratio of 1: 1-1.2, stirring for 30-40 min at the temperature of 20-25 ℃ and the stirring speed of more than 500r/min, centrifuging at 4000r/min, taking the solid, washing the solid by adopting the absolute ethyl alcohol, freeze-drying for 4-5 h at the temperature of-30-50 ℃, and crushing to obtain the nano calcium.
Preferably, the organic acid in the first step is any one of lactic acid, acetic acid and rice vinegar.
Preferably, the time interval between the 5 baking temperatures in the first step is not more than 2 min.
Preferably, in the step one, the eggshell is crushed by a ball mill.
Preferably, the drying process at 5 temperatures in the step one adopts a plurality of liquid spraying ovens, and each liquid spraying oven comprises:
a baking oven body;
the acid liquor tank is arranged in the containing cavity of the oven body, a liquid outlet pipe is arranged on the acid liquor tank, a micro water pump is arranged on the liquid outlet pipe, and the micro water pump is arranged in a heat insulation shell;
The plurality of spray heads are arranged at the top of the accommodating cavity of the oven body, are communicated with the liquid outlet pipe through pipe bodies and are arranged in a downward spraying direction;
a plurality of supports, a plurality of supports interval sets up in the holding cavity of oven body to all be located the shower nozzle below, every support includes:
the oven body comprises a pair of clamping groove bodies, wherein openings of the clamping groove bodies are oppositely arranged, the clamping groove bodies are rectangular, a rod body is fixedly connected to the opposite side walls of the clamping groove bodies, the rod body of one clamping groove body is fixed to the inner side wall of the accommodating cavity of the oven body through a bearing, the rod body of the other clamping groove body is fixed to an output shaft of a motor through a coupler, the motor is fixed to the other inner side wall of the accommodating cavity of the oven body, and an electromagnet is arranged at the bottom of the cavity of the clamping groove body;
the clamping device comprises an inner pipe and an outer pipe, wherein one end of the inner pipe and one end of the outer pipe are respectively fixed with a cuboid-shaped iron block, the iron block is matched with the shape of a clamping groove body, the iron block is accommodated in the clamping body, the other end of the inner pipe is slidably sleeved in the outer pipe, annular bulges are fixedly sleeved on the inner pipe and the outer pipe respectively, a pressure spring is sleeved between the two bulges, a plurality of insertion rods are arranged on the opposite sides of the two bulges at equal intervals, and the insertion rods on each bulge form a cylindrical ring shape;
The round roller is of a hollow structure, the round roller is coaxially sleeved on the inner pipe and the outer pipe, the protrusions and the pressure springs are accommodated in the inner cavity of the round roller, the inner sides of two end faces of the round roller are coaxially provided with a cylindrical annular inserting body, the inserting body is provided with a plurality of cylindrical inserting grooves at equal intervals, and the inserting grooves correspond to the inserting rods one by one;
when the two iron blocks are respectively abutted against the two electromagnets, the pressure spring is in a compressed state, one end of the inner pipe is sleeved in the outer pipe, and the plurality of inserting rods are inserted into the plurality of inserting grooves in a one-to-one correspondence manner;
the pair of support rings are oppositely sleeved on the outer side wall of the circular roller, a fixed rod is arranged between the pair of support rings, and a plurality of fixing rings are arranged on the circumferential side wall of each support ring and the fixed rod at intervals;
accept the dictyosome, it is the network structure who makes flexibility by flexible iron wire, it is the class rectangle to accept the dictyosome, the equal interval in circumference edge of accepting the dictyosome is equipped with a plurality of couples, accept the dictyosome and form double-deck dictyosome after folding along one of them central line, double-deck dictyosome along the length of this central line direction of perpendicular to with the girth of support ring outer loop equals, the eggshell lay flat in double-deck dictyosome, a plurality of couples one-to-one articulate on a plurality of solid fixed rings.
The nano calcium is prepared by the production method, the particle size of the nano calcium is less than 1000nm, the calcium content of the nano calcium is more than 15%, and the solubility of the nano calcium in water at 20-40 ℃ is more than 6g/100 ml.
Provides a food containing nano calcium, which comprises the nano calcium and food ingredients or additives or nutritional functional food or health-care food.
Provides the application of the nano calcium in preparing products for increasing the bone mineral density.
The invention at least comprises the following beneficial effects:
firstly, the production method of the nano calcium is simple, and the prepared nano calcium has small particle size, high solubility and easy absorption.
Secondly, in the eggshell drying process, the calcium content in the nano calcium can be improved by adopting multi-temperature section drying.
Thirdly, in the process of drying the eggshells, the calcium content in the nano calcium can be improved by spraying the organic acid.
Fourthly, in the eggshell drying process, after the interval time between the temperatures of two adjacent phases exceeds 2min, the calcium content of the calcium in the calcium rice can be influenced.
Fifthly, the liquid spraying oven can carry out liquid spraying operation without opening the oven door, so that temperature fluctuation caused by opening and closing of the oven door is avoided, the eggshells can be heated more uniformly up and down by arranging the round roller, the support ring and the motor to rotate, and the drying quality is ensured.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
Fig. 1 is a schematic structural diagram of the front side of the liquid spraying oven in one technical scheme of the invention;
FIG. 2 is a detail view of the stent of one embodiment of the present invention;
fig. 3 is a detailed view of the receiving net body according to one embodiment of the present invention.
Detailed Description
The present invention is further described in detail below with reference to the drawings and examples so that those skilled in the art can practice the invention with reference to the description.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials, if not otherwise specified, are commercially available; in the description of the present invention, the terms indicating orientation or positional relationship are based on the orientation or positional relationship shown in the drawings only for the convenience of description and simplification of description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
< example 1>
The production method of the high-absorption nano calcium comprises the following steps:
step one, cleaning eggshells with water, alkali liquor and water in sequence, then baking the eggshells for 3min, 8min, 3min and 3min at 55 ℃, 90 ℃, 170 ℃, 90 ℃ and 45 ℃ in sequence, spraying organic acid on the surfaces of the eggshells every 20s in the drying process of 5 temperatures, then crushing the baked eggshells to obtain eggshell powder, adding 1 time of organic acid of the quality of the eggshell powder into the eggshell powder, and soaking the eggshell powder in sequence at 20 ℃, 38 ℃, 60 ℃, 80 ℃ and 38 ℃ for 2h, 4h, 18h, 15h and 4h respectively, and then filtering and collecting a calcium-containing acid solution;
wherein the alkali liquor is sodium bicarbonate water solution with the mass fraction of 3%, the grain diameter of the eggshell powder is smaller than 100 meshes, the type of the organic acid for spraying is the same as that of the organic acid for soaking, and the using amount of the organic acid is 0.3 percent of the eggshell mass each time the organic acid is sprayed;
and step two, adding absolute ethyl alcohol into the calcium-containing acid solution according to the mass ratio of 1:1, stirring for 30min at the temperature of 20 ℃ and the stirring speed of 500r/min, centrifuging at the speed of 4000r/min, taking the solid, washing the solid by adopting the absolute ethyl alcohol, freeze-drying for 4h at the temperature of-30 ℃, and crushing to obtain the nano calcium.
Wherein the organic acid in the first step is lactic acid.
In the first step, the interval time between 5 baking temperatures is 1.5 min.
And in the first step, eggshells are crushed by adopting a ball mill.
< example 2>
The production method of the high-absorption nano calcium comprises the following steps:
step one, cleaning eggshells with water, alkali liquor and water in sequence, then baking the eggshells for 5min, 10min, 5min and 5min at 60 ℃, 100 ℃ and 50 ℃ in sequence, spraying organic acid on the surfaces of the eggshells every 30s in the drying process of 5 temperatures, then crushing the baked eggshells to obtain eggshell powder, adding organic acid with the mass being 2 times that of the eggshell powder into the eggshell powder, and soaking the eggshell powder in sequence at 25 ℃, 42 ℃, 65 ℃, 90 ℃ and 42 ℃ for 3h, 5h, 20h, 18h and 5h respectively, and then filtering and collecting a calcium-containing acid solution;
wherein the alkali liquor is a sodium bicarbonate water solution with the mass fraction of 5%, the grain diameter of the eggshell powder is smaller than 100 meshes, the type of the organic acid for spraying is the same as that of the organic acid for soaking, and the amount of the organic acid is 0.5 percent of the eggshell mass each time the organic acid is sprayed;
and step two, adding absolute ethyl alcohol into the calcium-containing acid solution according to the mass ratio of 1:1.2, stirring for 40min at 25 ℃ and the stirring speed of 800r/min, centrifuging at 4000r/min, taking the solid, washing the solid by adopting the absolute ethyl alcohol, freeze-drying for 5h at-50 ℃, and crushing to obtain the nano calcium.
Wherein the organic acid in the first step is lactic acid.
In the first step, the interval time between 5 baking temperatures is 2 min.
And in the first step, eggshells are crushed by adopting a ball mill.
< example 3>
The production method of the high-absorption nano calcium comprises the following steps:
step one, cleaning eggshells with water, alkali liquor and water in sequence, then baking the eggshells for 4min, 9min, 4min and 4min at 55 ℃, 95 ℃, 175 ℃, 95 ℃ and 50 ℃ in sequence, spraying organic acid on the surfaces of the eggshells every 25s in the drying process of 5 temperatures, then crushing the baked eggshells to obtain eggshell powder, adding organic acid with the mass 1.5 times that of the eggshell powder into the eggshell powder, and soaking the eggshell powder in sequence at 25 ℃, 40 ℃, 65 ℃, 85 ℃ and 40 ℃ for 2.5h, 4.5h, 19h, 16.5h and 4.5h respectively, and then filtering and collecting a calcium-containing acid solution;
wherein the alkali liquor is a sodium bicarbonate water solution with the mass fraction of 4%, the grain diameter of the eggshell powder is smaller than 100 meshes, the type of the organic acid for spraying is the same as that of the organic acid for soaking, and the using amount of the organic acid is 0.4% of the eggshell mass each time the organic acid is sprayed;
and step two, adding absolute ethyl alcohol into the calcium-containing acid solution according to the mass ratio of 1:1.1, stirring for 35min at 25 ℃ and the stirring speed of 500r/min, centrifuging at 4000r/min, taking the solid, washing the solid by adopting the absolute ethyl alcohol, freeze-drying for 4.5h at-40 ℃, and crushing to obtain the nano calcium.
Wherein the organic acid in the first step is lactic acid.
In the first step, the interval time between 5 baking temperatures is 2 min.
And in the first step, eggshells are crushed by adopting a ball mill.
< example 4>
The method for producing high absorption nano calcium is the same as that of example 3, except that the organic acid in the first step is acetic acid.
< example 5>
The method for producing high absorption nano calcium is the same as example 3, wherein the difference is that the organic acid in the step one is rice vinegar.
< example 6>
The process for producing high absorption nano calcium is the same as that of example 3, except that in the first step, the drying process at 5 temperatures is carried out by using liquid spraying ovens, and each liquid spraying oven comprises:
an oven body 1;
the acid liquor tank 2 is arranged in the accommodating cavity of the oven body 1, a liquid outlet pipe 21 is arranged on the acid liquor tank 2, a micro water pump is arranged on the liquid outlet pipe 21, and the micro water pump is arranged in a heat insulation shell; the acid liquid tank 2 is used for containing organic acid, such as lactic acid, and the lactic acid can flow out from the liquid outlet pipe 21 after the micro water pump is started.
The plurality of spray heads 3 are arranged at the top of the accommodating cavity of the oven body 1, the spray heads 3 are communicated with the liquid outlet pipe 21 through pipe bodies, and the spraying directions are arranged downwards; the lactic acid flows from the liquid outlet pipe 21 to the spray head 3 and flows out in a spray form, so that the lactic acid is sprayed in a state of small particle size.
The plurality of brackets 4 are arranged in the accommodating cavity of the oven body 1 at intervals and are all positioned below the spray head 3, and the brackets 4 are used for fixing the washed eggshells.
Each of the brackets 4 includes:
the oven comprises a pair of clamping groove bodies 5, wherein openings of the clamping groove bodies 5 are oppositely arranged, the clamping groove bodies 5 are cuboid, a rod body 51 is fixedly connected to the opposite side walls of the clamping groove bodies 5, the rod body 51 of one clamping groove body 5 is fixed to the inner side wall of an accommodating cavity of the oven body 1 through a bearing 52 to realize rotary connection, the rod body 51 of the other clamping groove body 5 is fixed to the output shaft of a motor 53 through a coupler, after the motor 53 is started, the motor 53 drives the rod body 51 to rotate so as to drive the clamping groove bodies 5 to rotate, the motor 53 is fixed to the other inner side wall of the accommodating cavity of the oven body 1, and an electromagnet 54 is arranged at the bottom of the cavity of the clamping groove body 5;
inner tube 6 and outer tube 7, the inner tube 6 with the one end of outer tube 7 is fixed with the iron plate 61 of a long cubic respectively, iron plate 61 with the shape matching of joint cell body 5, iron plate 61 holds in the joint is internal, and when electro-magnet 54 circular telegram, the firm magnetism of iron plate 61 is attracted on electro-magnet 54 to fixed inner tube 6 and outer tube 7, when electro-magnet 54 outage, lose the magnetic attraction effect, thereby can take off inner tube 6 and outer tube 7, the other end sliding sleeve of inner tube 6 is located in outer tube 7, makes inner tube 6 and outer tube 7 can slide each other, all fixed cover is equipped with annular arch 62 on inner tube 6 and the outer tube 7, is located that the cover is equipped with a pressure spring 63 between two arch 62, and the arch 62 can inject the coincidence length between inner tube 6 and the outer tube 7, when needing to take off inner tube 6 and outer tube 7 from joint cell body 5, the compression spring 63 needs to be compressed until the outer ends of the inner pipe 6 and the outer pipe 7 are separated from the clamping groove body 5, the inner pipe and the outer pipe can be taken down, a plurality of inserting rods 64 are arranged on the opposite side surfaces of the two bulges 62 at equal intervals, and the plurality of inserting rods 64 on each bulge 62 form a cylindrical ring shape;
The round roller 8 is of a hollow structure, the round roller 8 is coaxially sleeved on the inner pipe 6 and the outer pipe 7, the protrusion 62 and the pressure spring 63 are accommodated in a cavity inside the round roller 8, the inner sides of two end faces of the round roller 8 are coaxially provided with a cylindrical annular insertion body 81, the insertion body 81 is provided with a plurality of cylindrical insertion slots 82 at equal intervals, and the plurality of insertion slots 82 correspond to the plurality of insertion rods 64 one by one; after the slot 82 is connected with the inserted bar 64, when the clamping groove body 5 rotates, the inner pipe 6 or the outer pipe 7 can be driven to rotate, then the round roller 8 is driven to rotate, and then the outer pipe 7 or the inner pipe 6 is driven to rotate, so that the linkage effect is realized.
When the two iron blocks 61 abut against the two electromagnets 54 respectively, the compression spring 63 is in a compressed state, one end of the inner tube 6 is sleeved in the outer tube 7, and the plurality of insertion rods 64 are inserted into the plurality of slots 82 in a one-to-one correspondence manner;
the pair of support rings 9 are oppositely sleeved on the outer side wall of the round roller 8, a fixed rod is arranged between the pair of support rings 9, and a plurality of fixing rings 91 are arranged on the circumferential side wall of each support ring 9 and the fixed rod at intervals;
accept dictyosome 10, it makes flexible network structure for by flexible iron wire, accept dictyosome 10 and be the class rectangle, the equal interval in circumference edge of accepting dictyosome 10 is equipped with a plurality of couples 11, accept dictyosome 10 along the folding double-deck dictyosome that forms of one of them central line, double-deck dictyosome along the length of this central line direction of perpendicular to with the girth of the outer loop of support ring 9 equals, the eggshell lay flat in the double-deck dictyosome, a plurality of couples 11 one-to-one articulate on a plurality of solid fixed rings 91. Form certain distance space to support ring 9 surface and round roller 8, make and install and accept dictyosome 10 and the outer surface of round roller 8 on the support ring 9 and form the interval to be favorable to thermal infiltration, when the eggshell adorned between the double-deck dictyosome, starter motor 53 rotated, also was favorable to thermal infiltration more evenly, and was favorable to lactic acid to spray evenly, need not to open the oven door in addition and carries out the hydrojet operation, can avoid the temperature fluctuation that the opening and closing of oven door and arouse.
When a plurality of liquid spraying drying ovens exist, for example, 5 liquid spraying drying ovens can be used, 5 required temperatures can be set for each liquid spraying drying oven, after one drying temperature is finished, the motor 53 and the electromagnet 54 can be turned off, the inner tube 6 and the outer tube 7 are taken down and timely installed in the liquid spraying drying oven at the next temperature, the inner tube 6 and the outer tube 7 are inserted into the clamping groove body 5, the electromagnet 54 and the motor 53 are started, and therefore the gap between two adjacent drying temperatures can be guaranteed not to exceed 2min, and the influence on the calcium content of the nano calcium caused by the fact that the interval time between two adjacent temperatures exceeds 2min is avoided.
< comparative example 1>
The production method of high absorption nano calcium is the same as that of example 3, except that only one temperature is adopted to dry the eggshells in the first step, the drying temperature is 95 ℃, the time is 30min, and lactic acid is sprayed on the surfaces of the eggshells every 25s in the drying process.
< comparative example 2>
The production method of high absorption nano calcium is the same as example 3, except that no lactic acid is sprayed during the drying process at 5 temperatures in the first step.
< comparative example 3>
The production method of high absorption nano calcium is the same as that of example 3, except that the interval time between the 5 baking temperatures in the first step is 5 min.
< physical and chemical tests of Nano-calcium >
The particle size, the calcium content and the solubility of the nano-calcium in water at 20-40 ℃ of the nano-calcium prepared by the preparation methods of examples 1-6 and comparative examples 1-3 were measured, wherein the particle size of the prepared nano-calcium is less than 1000nm, and the calcium content and the solubility are shown in the following table:
TABLE 1 calcium content and solubility in Water of Nano-calcium
Group of Content of calcium% 20℃g/100ml 30℃g/100ml 40℃g/100ml
Example 1 15.24 6.35 7.53 10.05
Example 2 15.17 6.52 7.34 10.13
Example 3 15.08 6.19 7.42 10.02
Example 4 21.47 36.55 34.43 33.29
Example 5 19.71 35.25 35.76 34.28
Example 6 15.12 6.33 7.46 10.10
Comparative example 1 13.32 6.08 7.33 10.00
Comparative example 2 12.05 6.11 7.38 10.05
Comparative example 3 12.81 6.15 7.40 10.03
As can be seen from the above table, the calcium content of the nano-calcium prepared in examples 1 to 6 is above 15%, and the solubility in water at 20 to 40 ℃ is greater than 6g/100 ml.
In the process of drying eggshells, the content of calcium in the nano calcium can be improved by adopting multi-temperature-section drying in the comparison of the comparative example 1 and the example 3.
As can be seen from comparison between comparative example 2 and example 3, the content of calcium in the nano calcium can be increased by spraying the organic acid during the process of drying the eggshell.
Comparing comparative example 3 with example 3, it can be seen that the calcium content of the nano calcium is affected after the interval time between the temperatures of the two adjacent phases exceeds 2min in the eggshell drying process.
< nano-calcium production test >
1. The nano-calcium prepared in example 3 was added to flour to prepare high calcium flour.
2. The nano-calcium prepared in the example 4 is mixed with filler, adsorbent, adhesive, lubricant, dispersant, wetting agent, disintegrating agent, perfume and pigment to prepare meal replacement powder.
4. And (3) dissolving and uniformly mixing the nano calcium prepared in the example 5 with a flavoring agent, a bacteriostatic agent, an antioxidant, a coloring agent and water, and preparing the nano calcium oral liquid.
< Nano calcium function test >
Female rats (260-280 g in weight) are randomly selected and divided into 6 groups, wherein the 6 groups are respectively a control group, a model group, a calcium carbonate feed group, a nano-calcium feed group I prepared in example 3, a nano-calcium feed group II prepared in example 4, a nano-calcium feed group III prepared in example 5, and 10 rats in each group.
During the whole feeding period, the control group is fed with common daily ration of rats, and the rest groups are fed with common daily ration of rats and are injected with dexamethasone (1mg/kg) for 1 time and 4 weeks at intervals of 2 days, so as to establish the osteoporosis model. And stopping injecting dexamethasone from the 5 th week, wherein the model group feed is continuously fed with common daily ration, and the calcium carbonate feed group, the nano-calcium feed group I, the nano-calcium feed group II and the nano-calcium feed group III are respectively fed with calcium carbonate daily ration (containing 20mg/100g of calcium), the daily ration containing the nano-calcium prepared in example 3, the daily ration containing the nano-calcium prepared in example 4 and the daily ration containing the nano-calcium prepared in example 5, wherein the content of the nano-calcium in the daily ration is 100mg/100g, which is equivalent to that of the daily ration containing 15-21 mg/100g of calcium. During the test period, rats were given deionized water to avoid calcium pick-up from the drinking water and were fed for a total of 10 weeks.
The results of bone density measurements using dual energy X-ray absorption from rat femurs are shown in the following table:
TABLE 2 bone Density of femur of rat
Group of Bone density of upper end of femur is kg/cm2 Density of lower femur bone kg/cm2
Control group 0.131 0.193
Model set 0.106 0.152
Calcium carbonate feed group 0.115 0.162
Nano calciumFeed group I 0.120 0.173
Nano calcium feed group II 0.127 0.189
Nanometer calcium feed group III 0.125 0.185
As shown in table 2, when the control group and the model group are compared, the bone density of the upper end of the femur and the bone density of the lower end of the femur of the rat in the model group are both significantly lower than those of the upper end of the femur and the lower end of the femur of the rat in the control group, which indicates that the osteoporosis model of the rat is successfully constructed.
As can be seen from comparison of the nano-calcium feed group I, the nano-calcium feed group II and the nano-calcium feed group III with the model group, the bone density at the upper end of the femur and the bone density at the lower end of the femur of the rats of the nano-calcium feed group I, the nano-calcium feed group II and the nano-calcium feed group III are both significantly improved and are close to those of the rats of the control group, which indicates that the nano-calcium prepared in examples 3 to 5 has the effect of increasing the bone density of the rats.
Compared with the calcium carbonate feed group, the nano calcium feed group I, the nano calcium feed group II and the nano calcium feed group III show that the recovery of the bone density at the upper end and the bone density at the lower end of the femur of rats of the nano calcium feed group I, the nano calcium feed group II and the nano calcium feed group III is closer to that of the control group than that of the calcium carbonate feed group, which shows that the effect of increasing the bone density of rats prepared in the examples 3-5 is obviously better than that of the calcium carbonate feed group, and indirectly shows that the nano calcium prepared in the examples 3-5 is easier to be absorbed by the rats.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (8)

1. The production method of the high-absorption nano calcium is characterized by comprising the following steps:
step one, cleaning eggshells with water, alkali liquor and water in sequence, then baking the eggshells at 55-60 ℃, 90-100 ℃, 170-180 ℃, 90-100 ℃ and 45-50 ℃ for 3-5 min, 8-10 min, 3-5 min and 3-5 min respectively, spraying organic acid on the surfaces of the eggshells every 20-30 s in the drying process of 5 temperatures, then crushing the baked eggshells to obtain eggshell powder, adding organic acid with the mass 1-2 times of that of the eggshell powder into the eggshell powder, soaking the eggshell powder for 2-3 h, 4-5 h, 18-20 h, 15-18 h and 4-5 h at the temperature of 20-25 ℃, 38-42 ℃, 60-65 ℃, 80-90 ℃ and 38-42 ℃ in sequence, and then filtering and collecting an acid solution containing calcium;
Wherein the alkali liquor is a sodium bicarbonate water solution with the mass fraction of 3-5%, the particle size of the eggshell powder is smaller than 100 meshes, the organic acid for spraying and the organic acid for soaking are the same in type, and the amount of the organic acid is 0.3-0.5% of the eggshell mass each time the organic acid is sprayed;
and secondly, adding absolute ethyl alcohol into the calcium-containing acid solution according to the mass ratio of 1: 1-1.2, stirring for 30-40 min at the temperature of 20-25 ℃ and the stirring speed of more than 500r/min, centrifuging at 4000r/min, taking the solid, washing the solid by adopting the absolute ethyl alcohol, freeze-drying for 4-5 h at the temperature of-30-50 ℃, and crushing to obtain the nano calcium.
2. The method for producing highly absorbable nano calcium as claimed in claim 1, wherein the organic acid in the first step is any one of lactic acid, acetic acid and rice vinegar.
3. The method for producing highly absorbing nano-calcium as claimed in claim 1, wherein the time interval between the 5 baking temperatures in the first step is not more than 2 min.
4. The method for producing highly absorbing nano-calcium as claimed in claim 1, wherein the eggshell is pulverized by a ball mill in the first step.
5. The method for producing high absorption nano calcium as claimed in claim 1, wherein the drying process at 5 temperatures in the first step is performed by using a plurality of spray ovens, each spray oven comprising:
A baking oven body;
the acid liquor tank is arranged in the containing cavity of the oven body, a liquid outlet pipe is arranged on the acid liquor tank, a micro water pump is arranged on the liquid outlet pipe, and the micro water pump is arranged in a heat insulation shell;
the plurality of spray heads are arranged at the top of the accommodating cavity of the oven body, are communicated with the liquid outlet pipe through pipe bodies and are arranged in a downward spraying direction;
a plurality of supports, a plurality of supports interval sets up in the holding cavity of oven body to all be located the shower nozzle below, every support includes:
the oven body comprises a pair of clamping groove bodies, wherein openings of the clamping groove bodies are oppositely arranged, the clamping groove bodies are rectangular, a rod body is fixedly connected to the opposite side walls of the clamping groove bodies, the rod body of one clamping groove body is fixed to the inner side wall of the accommodating cavity of the oven body through a bearing, the rod body of the other clamping groove body is fixed to an output shaft of a motor through a coupler, the motor is fixed to the other inner side wall of the accommodating cavity of the oven body, and an electromagnet is arranged at the bottom of the cavity of the clamping groove body;
the clamping device comprises an inner pipe and an outer pipe, wherein one end of the inner pipe and one end of the outer pipe are respectively fixed with a cuboid-shaped iron block, the iron block is matched with the shape of a clamping groove body, the iron block is accommodated in the clamping body, the other end of the inner pipe is slidably sleeved in the outer pipe, annular bulges are fixedly sleeved on the inner pipe and the outer pipe respectively, a pressure spring is sleeved between the two bulges, a plurality of insertion rods are arranged on the opposite sides of the two bulges at equal intervals, and the insertion rods on each bulge form a cylindrical ring shape;
The round roller is of a hollow structure, the round roller is coaxially sleeved on the inner pipe and the outer pipe, the protrusions and the pressure springs are accommodated in the inner cavity of the round roller, the inner sides of two end faces of the round roller are coaxially provided with a cylindrical annular inserting body, the inserting body is provided with a plurality of cylindrical inserting grooves at equal intervals, and the inserting grooves correspond to the inserting rods one by one;
when the two iron blocks are respectively abutted against the two electromagnets, the pressure spring is in a compressed state, one end of the inner pipe is sleeved in the outer pipe, and the plurality of inserting rods are inserted into the plurality of inserting grooves in a one-to-one correspondence manner;
the pair of support rings are oppositely sleeved on the outer side wall of the circular roller, a fixed rod is arranged between the pair of support rings, and a plurality of fixing rings are arranged on the circumferential side wall of each support ring and the fixed rod at intervals;
accept the dictyosome, it is the network structure who makes flexibility by flexible iron wire, it is the class rectangle to accept the dictyosome, the equal interval in circumference edge of accepting the dictyosome is equipped with a plurality of couples, accept the dictyosome and form double-deck dictyosome after folding along one of them central line, double-deck dictyosome along the length of this central line direction of perpendicular to with the girth of support ring outer loop equals, the eggshell lay flat in double-deck dictyosome, a plurality of couples one-to-one articulate on a plurality of solid fixed rings.
6. The nano calcium is characterized by being prepared by the production method of any one of claims 1 to 4, the particle size of the nano calcium is less than 1000nm, the calcium content of the nano calcium is more than 15%, and the solubility of the nano calcium in water at 20-40 ℃ is more than 6g/100 ml.
7. Food containing nano-calcium, characterized by comprising nano-calcium according to claim 6 and food ingredients or additives or nutritional functional food or health food.
8. Use of the nano-calcium of claim 6 for the preparation of a product for increasing bone density.
CN202010516426.8A 2020-06-09 2020-06-09 Production method of high-absorption nano calcium, product and application thereof Pending CN111838680A (en)

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