CN1189338A - Complexing calcium and its prodn. method - Google Patents

Complexing calcium and its prodn. method Download PDF

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CN1189338A
CN1189338A CN98100813A CN98100813A CN1189338A CN 1189338 A CN1189338 A CN 1189338A CN 98100813 A CN98100813 A CN 98100813A CN 98100813 A CN98100813 A CN 98100813A CN 1189338 A CN1189338 A CN 1189338A
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calcium
bone
complex
reaction kettle
temperature
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CN1069031C (en
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陈勇
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Shandong Guangrun Bioengineering Co., Ltd.
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陈勇
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Abstract

A complex calcium as calcium supplementing preparation or food, or edible additive for food is a water-soluble calcium product, which is prepared from fresh animal bone through using alkaline enzyme to act on said bone to make it become the mixture of molecular calciums, reaction with diluted acid to obtain soluble ion-type calcium, and complexing with amino acids necessary for human body under the action of acidic protease.

Description

Complex calcium and method for producing same
The invention relates to a novel calcium product-complex calcium and a manufacturing method thereof, which takes fresh animal bones as raw materials, and leads calcium element in aggregate to exist in the form of complex under the action of enzyme, thereby being fully absorbed and effectively utilized by human bodies.
Calcium is an element with very active chemical properties, cannot exist in the form of an 'element' or an 'atom' in nature, but only exists in the form of a compound, and is divided into three states, namely a molecular state, an ionic state and a complex state according to thedegree of combination of calcium and other ions in the compound.
Calcium is one of the most abundant elements in human body, and accounts for about 1.5-2% of the weight of human body, wherein about 99% of calcium exists in bones and teeth, and 1% of calcium exists in blood, extracellular fluid and soft tissue cells. Calcium is involved in almost all vital activities in the human body. Plays a very important and even key role in maintaining the functions of nerves, circulation, respiration, digestion, endocrine, muscles, urinary, immunity, reproduction and the like of a human body, and in the physiological processes of nerve impulse transmission, muscle stress, cardiac rhythm maintenance, blood coagulation, cell adhesion and the like.
Calcium deficiency is common in humans, and has two causes: first, the human body cannot produce calcium by itself and can only ingest it from the diet. The common, varying degree of lack of calcium throughout humans results from differences in food structure and differences in absorption. Studies have shown that 1/2 adult women, 1/3 children under 10 years and 2/3 elderly over 60 years are calcium deficient in the united states alone; in China, as the main food of people is cereals and the calcium content of the cereals is very low, the phenomenon of calcium deficiency of Chinese people is more common and serious, and the investigation shows that the daily calcium deficiency of China reaches 250-350 mg. Second, calcium in the human body is continuously lost as the human ages. Experts believe that a person is in a calcium balance period between 20 and 35 years old, a calcium increment period before 20 years old and a calcium loss period after 35 years old, and the loss rate of calcium is accelerated, and the average annual loss rate is about 1%.
Calcium deficiency has various effects on human body resistance, endurance, immunity, memory, comprehension, creativity, reaction ability and anti-aging ability. Furthermore, diseases such as hyperosteogeny, osteoporosis, fracture, rickets, dental caries, scapulohumeral periarthritis, arthritis, childhood mental retardation, senile dementia, hypertension, heart disease, diabetes, anemia, anorexia and the like have direct or indirect relationship with calcium deficiency.
The importance of calcium in human activities is increasingly being emphasized, and various calcium products are continuously coming out. The current calcium product market has two aspects of international and domestic, and as far as international is concerned, the main product is CoralCalcum of American Health move company; oyster Shell Calcium from Stanley Pharmaceutical, Canada; skim Delux Calcum from the company Undenhallla borarates, France; and Calcichew- -D from Nycomed Pharma, Norway3And the like. The international market is characterized by a few product types but large market share.
The domestic calcium product market is just opposite, and according to incomplete statistics, 68 enterprises which only take calcium products as main products exist, and more than 100 types of products are counted.
Although these calcium products are of a wide variety, there are two main types of products in terms of their product types:
molecular calcium: such as calcium carbonate, calcium lactate, etc.
Ionic calcium: such as active calcium, high-efficiency calcium, etc.
Research proves that when a human body absorbs calcium, molecular calcium needs to consume enzymes of the human body, so that the molecular calcium cannot be completely absorbed in the human body; the ionized calcium reacts with oxalic acid and phytic acid in the stomach of a human body to generate insoluble precipitates, so that the ionized calcium is difficult to be completely absorbed by the human body; only the complex calcium does not react with acidic substances in the stomach of the human body and does not consume enzymes of the human body, so the complex calcium is very easy to be completely absorbed by the human body.
The product and the production process of the complex calcium are not reported.
One prior application of the present inventor, application No. 921135320.3, discloses a method for preparing high-calcium bone meal which uses fresh animal bone as raw material and makes all the nutrient components in the bone material be fully absorbed by human body by means of biological activation processing. As a calcium product or food additive, the absorption rate of the calcium in the calcium product or food additive is higher than that of other calcium food additives. However, the calcium in the high-calcium bone powder prepared by the method is still in an ionic form and still is difficult to be completely absorbed by a human body strictly.
The invention aims to provide a complex calcium product which can be used as a calcium supplement preparation or calcium food and can also be used as an additive for food processing.
The other purpose of the invention is to make the calcium in the fresh animal bone from molecular → ionic → complex type by enzyme engineering method, so as to make the human body absorb and utilize better.
The complex calcium provided by the invention is a soluble calcium product formed by complexing ionic calcium with amino acid under the action of enzyme.
The complex calcium provided by the invention is prepared by taking bone slurry of fresh animal bones as a raw material, hydrolyzing the bone slurry into calcium in a molecule form by using alkaline enzyme, hydrolyzing the calcium in the molecule form intoionic calcium by using edible dilute acid, and then reacting the ionic calcium with amino acid under the action of acid protease to form the complex calcium.
The preparation method of complex calcium provided by the invention is that fresh animal bones are processed into bone pulp A through the procedures of cleaning, pulp grinding and the like1Then the following operations are carried out: (1) mixing the bone slurry A1Feeding into a stage I reaction kettle, controlling the reaction temperature at 25-35 ℃, adding bacillus subtilis while slowly stirring, wherein the weight of the biological protein is 0.2-0.4% of that of bone slurry, and preserving heat for 20-40 minutes to obtain bone slurry A2(ii) a (2) Mixing the bone slurry A2Feeding the mixture into a II-stage reaction kettle, reacting at the temperature of 30-40 ℃, adding alkaline protease accounting for 0.3-0.5% of the weight of the bone slurry, and keeping the temperature for 40-60 minutes to obtain bone slurry A3(ii) a (3) Mixing the bone slurry A3Is sent intoAnd (3) adding alkaline lipase into a third-stage reaction kettle at the reaction temperature of 60-70 ℃, wherein the addition amount of the alkaline lipase is 0.4-0.6 percent of the weight of the bone slurry, and keeping the temperature for 20-30 minutes to obtain the bone slurry A4(ii) a (4) Mixing the bone slurry A4Feeding into a stage IV reaction kettle, adding a proper amount of water, keeping the temperature at 60-70 ℃, adding edible dilute acid to ensure that the pH of the reaction material is less than or equal to 2, keeping the temperature for 40-50 minutes, and separating out liquid B0(ii) a (5) The residual residue is sent into a V-stage reaction kettle, and the operation and the reaction in the IV-stage reaction kettle are repeated to ensure that the residual residue is completely dissolved into liquid B1(ii) a (6) And mixing the liquid B1、B0Combining and feeding into a VI-grade reaction kettle, keeping the temperature at 60-70 ℃, respectively adding amino acid accounting for 8-12% of the weight of the materials and acid protease accounting for 0.8-1.2% of the weight of the materials into the reaction kettle, and preserving the temperature for 30 minutes to obtain a complex calcium mixture C0(ii) a (7) Mixing the complex calcium with the mixture C0Processing into products according to requirements.
The raw material bone slurry A for producing the complex calcium of the invention1The animal bone is prepared by cleaning, removing and separating meat, muscle, bone oil and the like remained on bones of animal fresh bones with qualified quality inspection to obtain clean bones, and then carrying out bone crushing, grinding, sieving, homogenate and the like on the bones to obtain the animal boneAre common processing techniques and are not described in detail herein.
The main reaction mechanism of the invention is as follows:
in animal bones, calcium exists in the form of molecular compounds, and the content of calcium in different animal bones is approximately as follows:
bone species Pig Cattle Sheep (sheep)
Calcium content 2.8~3.5% 3.5~5.0% 3.0~4.5%
The calcium compound existing in molecular form can be converted into calcium in ionic form under the action of acid; calcium in ionic form forms a calcium complex under the action of acidic protease. When a human body absorbs calcium, the molecular calcium needs to consume enzymes of the human body, so that the molecular calcium cannot be completely absorbed in the human body; the ionized calcium reacts with oxalic acid and phytic acid in the stomach of a human body to generate insoluble precipitates, so that the ionized calcium is difficult to be completely absorbed by the human body; only the complex calcium does not react with acidic substances in the stomach of the human body and does not consume enzymes of the human body, so the complex calcium is very easy to be completely absorbed by the human body.
In the process method, bone slurry is changed into a mixture containing insoluble calcium molecules in the first, second and third-stage reaction kettles under the action of alkaline enzyme, the calcium compounds existing in molecular form react with acid in the fourth and V-stage reaction kettles to be converted into soluble ionic calcium, and the ionic calcium further forms soluble complex calcium under the action of acid protease.
The basic reaction process of the invention is as follows:
in I, II, III-grade reaction kettles, biomacromolecules such as collagen, phosphoprotein, fat and the like of sclerotin are mainly hydrolyzed into amino acid and other hydrolysis products under the action of enzyme, and the process is as follows: 1. opening of peptide bonds 2. Proton exchange
Wherein R 'and R' represent biomacromolecules such as collagen, phosphoprotein, fat and the like, in IV and V-grade reaction kettles, insoluble calcium salts such as calcium hydroxy phosphate and the like combined with the macromolecules are mainly reacted to generate soluble ionic calcium, and the basic process is as follows:
in the VI-level reaction kettle, soluble ionic calcium is re-complexed with amino acid and the like under the action of enzyme to form soluble complex calcium, and the basic process is as follows: r represents an amino acid
In the above-mentioned preparation method, the enzyme added into the first, second and third-stage reaction kettles is single alkaline enzyme, and for obtaining optimum reaction result, three different alkaline enzymes are respectively used, i.e. in the first-stage reaction kettle, the bacillus subtilis is used, in the second-stage reaction kettle, the alkaline protease, such as trypsin, peptidase and cellulose protease, is added, in the third-stage reaction kettle, the alkaline lipase is added, and the raw material bone is undergone the above-mentioned three hydrolysis reactions, so that it is the mixture containing molecular type calcium.
The edible dilute acid used in the invention is dilute hydrochloric acid, and aims to convert insoluble molecular calcium into soluble ionic calcium.
The enzyme added into the VI-stage reaction kettle is acidic protease for food or medicine, in order to ensure that the reaction material obtains enough enzyme activity, all ionic calcium is complexed with amino acid to obtain complex calcium, preferably mixed enzyme is used, namely more than two kinds of acidic protease are selected to be mixed for use, the mixing ratio is 1: 1-1: 1.25, for example, pepsin, papain, bromelain and the like are used.
The invention uses amino acid as a carrier of complex calcium, and in order to be beneficial to the absorption of human body, the invention preferably uses one of eight kinds of essential amino acids of human body, namely methionine, valine, leucine, isoleucine, lysine, threonine, tryptophan and phenylalanine.
The obtained mixture containing complex calcium can be further processed into calcium supplement preparations and calcium foods or used as food additives according to requirements to increase the calcium content in the foods, and because the calcium in the mixture is in a complex state, the calcium can be fully absorbed by human bodies no matter the mixture is directly eaten or added into the foods to prepare high-calcium foods.
The attached drawing is a process flow block diagram of the present invention.
In conclusion, the invention provides a novel calcium product and a manufacturing method thereof, and popularization and application of the novel calcium product have good promotion effects on improving the calcium deficiency condition of human beings, particularly Chinese people and improving the health level.
Examples
Cleaning fresh bone of cattle or sheep, removing residual meat, muscle and bone oil on bone, pulverizing,Grinding, sieving, and homogenizing to obtain bone slurry A1Mixing the bone slurry A1Feeding into a first-stage reaction kettle, controlling the reaction temperature at 30 + -2 deg.C, slowly stirring while adding Bacillus subtilis whose biological protein is 0.3% of the weight of bone slurry, and maintaining the temperature for about 30 min to obtain bone slurry A2(ii) a Mixing bone slurry A2Feeding into a second-stage reaction kettle, reacting at 35 + -2 deg.C, adding trypsin 0.4% of the weight of bone slurry, and maintaining for about 50 min to obtain bone slurry A3(ii) a Mixing bone slurry A3Feeding into a grade III reaction kettle, reacting at 65 + -2 deg.C, adding alkaline lipase in an amount of 0.5 wt% of bone slurry, and keeping the temperature for 30 min to obtain bone slurry A4(ii) a Mixing bone slurry A4Feeding into IV-stage reaction kettle, adding appropriate amount of water, maintaining the temperature at 65 + -2 deg.C, adding dilute hydrochloric acid to make the pH of the reaction material less than or equal to 2, maintaining the temperature for 40 min, and separating out liquid B0(ii) a The residual residue is sent into a V-stage reaction kettle, and the operation and the reaction in the IV-stage reaction kettle are repeated to ensure that the residual residue is completely dissolved into liquid B1(ii) a Mixing the liquid B1、B0Mixing, feeding into a VI-stage reaction kettle, keeping the temperature at 65 + -2 deg.C, adding valine 10 wt% of the reaction materials and mixed enzyme of pepsin and papain 1 wt% (the two enzymes are mixed at a ratio of 1: 1), and keeping the temperature for 30 min to obtain complex calcium mixture C0

Claims (7)

1. A complex calcium product, characterized in that the product is a soluble calcium product formed by complexing ionic calcium with amino acids under the action of an enzyme.
2. The calcium complex product as claimed in claim 1, wherein the calcium complex product is prepared by using bone slurry of fresh animal bone as raw material, hydrolyzing the bone slurry with alkaline enzyme to obtain calcium ion, hydrolyzing with dilute edible acid to obtain calcium ion, and complexing the calcium ion with amino acid under the action of acid protease.
3. A process for preparing the calcium complex product features that the fresh bone of animal is washed and groundProcessing the bone paste into bone paste A1Then the following operations are carried out: (1) mixing the bone slurry A1Feeding into a stage I reaction kettle, controlling the reaction temperature at 25-35 ℃, adding bacillus subtilis while slowly stirring, wherein the weight of the biological protein is 0.2-0.4% of that of bone slurry, and preserving heat for 20-40 minutes to obtain bone slurry A2(ii) a (2) Mixing the bone slurry A2Feeding the mixture into a II-stage reaction kettle, reacting at the temperature of 30-40 ℃, adding alkaline protease accounting for 0.3-0.5% of the weight of the bone slurry, and keeping the temperature for 40-60 minutes to obtain bone slurry A3(ii) a (3) Mixing the bone slurry A3Feeding the mixture into a III-grade reaction kettle, reacting at the temperature of 60-70 ℃, adding alkaline lipase in an amount of 0.4-0.6 percent of the weight of the bone slurry, and keeping the temperature for 20-30 minutes to obtain the bone slurry A4(ii) a (4) Mixing the bone slurry A4Feeding into a stage IV reaction kettle, adding a proper amount of water, keeping the temperature at 60-70 ℃, adding edible dilute acid to ensure that the pH of the reaction material is less than or equal to 2, keeping the temperature for 40-50 minutes, and separating out liquid B0(ii) a (5) The residual residue is sent into a V-stage reaction kettle, and the operation and the reaction in the IV-stage reaction kettle are repeated to ensure that the residual residue is completely dissolved into liquid B1(ii) a (6) And mixing the liquid B1、B0After being combined, the mixture is sent into a VI-level reaction kettle, the temperature is kept at 60-70 ℃, amino acid accounting for 8-12% of the weight of the materials and acid protease accounting for 0.8-1.2% of the weight of the materials are respectively added into the reaction kettle, and heat preservation is carried out for 30 minutes to obtain a complex calcium mixture C0(ii) a (7) Mixing the complex calcium with the mixture C0Processing into products according to requirements.
4. The method according to claim 3, wherein the enzymes added to the first, second and third reaction vessels are all single enzymes and alkaline enzymes.
5. A method of producing a calcium complex product according to claim 3 wherein the edible dilute acid used is dilute hydrochloric acid.
6. The method for producing a complex calcium product according to claim 3, wherein the amino acid is an essential amino acid for human body, i.e., methionine, valine, leucine, isoleucine, lysine, threonine, tryptophan, or phenylalanine.
7. The method for producing a complex calcium product according to claim 3, wherein the acidic protease added to the VI-stage reaction vessel is a food or pharmaceutical acidic protease, and two or more types of acidic proteases are used in combination at a ratio of 1: 1 to 1: 1.25.
CN 98100813 1998-02-16 1998-02-16 Complexing calcium and its prodn. method Expired - Lifetime CN1069031C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1131041C (en) * 1999-08-31 2003-12-17 内蒙古包头市东宝集团生物保健品有限公司 Instant aminoacid-calcium particles and preparing process thereof
CN101006857B (en) * 2006-01-26 2011-03-23 陈勇 Products of nutrients for bones and preparation method
CN103656626A (en) * 2013-12-12 2014-03-26 王爱景 Compound complexing calcium preparation for treating and nourishing bones for middle and old aged people and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1030369C (en) * 1992-12-05 1995-11-29 陈勇 Technology for making bone powder containing high-calcium

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1131041C (en) * 1999-08-31 2003-12-17 内蒙古包头市东宝集团生物保健品有限公司 Instant aminoacid-calcium particles and preparing process thereof
CN101006857B (en) * 2006-01-26 2011-03-23 陈勇 Products of nutrients for bones and preparation method
CN103656626A (en) * 2013-12-12 2014-03-26 王爱景 Compound complexing calcium preparation for treating and nourishing bones for middle and old aged people and preparation method thereof
CN103656626B (en) * 2013-12-12 2015-03-25 王爱景 Compound complexing calcium preparation for treating and nourishing bones for middle and old aged people and preparation method thereof

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Owner name: SHANDONG GUANGRUN BIOLOGY ENGINEERING CO., LTD.

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Address after: 100080 Beijing City, Haidian District Road No. 26 Haidian Guangrun biotechnology company

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