WO1995015293A1 - An ultra fine powder calcium oxide, preparation and use thereof - Google Patents

Abstract

The invention provides an ultra fine powder calcium oxide, wherein the oxide has a particle size of 10-6-10-9 m. The oxide is made from a calcium carbonate by the way of a plasma decomposition. The invention further provides a calcium - containing composition, wherein the composition has the ultra fine powder calcium oxide. The composition is usable to supply men and animals with the necessary calcium.

Description

 Ultrafine calcium oxide and preparation and application thereof

 The invention relates to an ultrafine calcium oxide powder and a preparation method thereof, and to a composition of ultrafine particle size (nanoscale) calcium oxide. Background of the invention

 Current research in the medical field shows that humans worldwide are facing an astonishing calcium deficiency. Calcium has the normal functions of maintaining circulation, breathing, nerves, digestion, endocrine, muscle, bone, urinary, and immunity in various systems of the human body. Important role. Calcium deficiency can cause a variety of diseases: Children with calcium deficiency can develop rickets, and are susceptible to colds, night crying, irritability, anorexia, constipation, chicken breasts, "

O "or" X "legs, etc .; calcium deficiency in pregnant women can cause backache, numbness of hands, feet, muscle spasms, severe cases of prenatal hypertension syndrome, postpartum tooth looseness, and affect the health of newborns Middle-aged and elderly people are as vulnerable to calcium deficiency as children. Hypertension in middle-aged and elderly people. Arrhythmias, diabetes, and ulcers are all related to calcium metabolism disorders. For countries and regions where daily food is still mainly plant-based foods, In China, for example, the calcium deficiency in plant foods is particularly serious because it is not easily absorbed by the body.

 At present, the active calcium that is popular in the market is a type of calcium oxide, which is prepared by using marine biological oysters and shells that have been calcined and pulverized at high temperature. It represents the highest level in the current calcium market and can be called the second generation calcium. However, there are two disadvantages. The first is that seawater is becoming increasingly polluted. Active calcium produced by this method will inevitably leave some heavy metal elements that are harmful to people's health in it. To this end, the active calcium produced by a developed western country specifically states: Non-marine biological shell made of raw materials. Obviously, the ideal source of calcium still needs further research and development! The measurement proved that the bioavailability of various active calcium on the international market is less than 30%. The second is the low calcium content of calcium on the market, only 10-55%. When making other finished products, additives are needed to make the calcium content of the commercially available calcium agent lower, which cannot meet the daily calcium intake required by the human body. Therefore, it is imperative to find a new and effective calcium agent which is easily absorbed by the human body. Summary of invention

 One of the objects of the present invention is to provide an ultrafine particle size calcium oxide powder.

 Another object of the present invention is to provide a calcium-containing composition which is easily absorbed by the human body.

Another object of the present invention is to provide a calcium-containing composition with high calcium content and high bioavailability. According to the present invention, an ultra-fine calcium oxide product has a fineness of less than 1 micron and an average fineness of 100 nm.

The invention also relates to a calcium-containing composition, which comprises an ultra-fine calcium oxide product with a fineness of 10 ′ ⁶ −1 (T ⁹ m).

 Other objects of the present invention will become apparent from the following detailed description of the present invention. The tube of the drawings is to be explained

 FIG. 1 is a schematic flow chart of preparing the ultrafine calcium oxide powder of the present invention by a plasma method; FIG. 2 is a particle size distribution curve diagram of the ultrafine calcium oxide powder in Example 1. FIG. Detailed description of the invention

 Since the calcium on the market currently cannot satisfy people's life and health requirements, the inventor of the present application has been working for many years to find a calcium-containing composition that has a high calcium content and is easily absorbed by the human body. In the research, the inventors found that reducing the particle size of calcium oxide to a certain range can increase the absorption of calcium by the human body and has high bioavailability.

Thus, according to the present invention, an oxide ultrafine calcium powder, the fineness of ^{ιο 'δ - io' 9 m} , or at least a fineness of 10 ^'6 - 10' ⁹ m in diameter accounted for 90% or more, preferably fineness of about 10- ⁷ m or less, ^{e.g., 10 '7 - 10' 8} m, or particle size of about ^10-7-- 70% or more of particles of 10 ^'8 m in. This ultra-fine calcium oxide powder is also referred to as nanometer calcium oxide in this specification because its fineness is on the order of nanometers.

 A method for preparing the ultra-fine calcium oxide powder includes decomposing the calcium carbonate powder by a plasma method. The equipment for generating the plasma is a commercially available equipment. The calcium carbonate powder used in this method is readily available on the market. This calcium carbonate powder can be derived from marine organisms or it can be obtained from other sources.

Referring to FIG. 1, raw calcium carbonate powder 1 is sent to a plasma reaction furnace 4 by a carrier gas 8. The average particle size of the calcium carbonate powder used is about 100 mesh or less, and the carrier gas may be a pressurized gas such as air or an inert gas. The use of pressurized gas as the carrier gas can help the raw materials move in the process, so the pressure of the carrier gas should be sufficient to maintain the flow state of the raw materials throughout the process. Generally, the pressure of the carrier gas is 0.5 atmosphere or more. The raw material 1 is in a plasma reaction furnace, and under the action of the energy provided by the plasma generator 3, the plasma 2 is decomposed to generate ultrafine particles of calcium oxide powder and carbon dioxide gas. The reaction temperature in the plasma reactor is controlled at 2000 ^e C or above.

The reaction product was collected in one stage 5 to obtain ultrafine particles of calcium oxide powder. For further recycling Superfine particles of calcium oxide powder can be set for secondary collection6. The carbon dioxide gas is discharged through the exhaust gas filtering system 7. The product can be collected by cooling cyclones, cloth bags and other common facilities.

According to the present invention, a product obtained by decomposing calcium carbonate by a plasma method has a particle size of about 10 ' ⁶ -10', or at least 90% of the particles have a particle size of 10 ' ⁶ -10' ⁹ m. Preferred particle size of about 10 · ¾ or more, e.g. 10 · ⁷ _10 · ¾ or at least 70% --80% of the particle size is 10 * or more, e.g., 10 ^"7 -10'm _o calcium oxide content in the product of about ⁹⁰ % or more, preferably 95% or more.

 Tests show that the ultra-fine calcium oxide powder of the present invention is easily absorbed by the human body, and its bioavailability can be as high as 40%. Therefore, the ultra-fine calcium oxide powder of the present invention can be used as a source of human or animal calcium, or used to supplement human or animal calcium alone or with other substances, and can be used as a component to be incorporated into other products, such as food. , Feed, nutrition or medicine, etc., can also be made into separate products to provide calcium to animals or humans.

According to the present invention, a calcium-containing composition, comprising a particle size of 10 · ⁶ - 10 Oxidation of calcium powder, and one or more physiologically acceptable excipients and / or adjuvants, preferably a particle size of 10 ^'7--10 '¾1 of calcium oxide. Or the calcium-containing composition contains other ultrafine calcium oxide of the present invention. The calcium oxide of the present invention should be contained in the composition in an amount sufficient to meet human and / or animal needs for calcium. In addition, trace elements useful for humans and / or animals can also be added to the composition, such as magnesium, selenium, strontium, fluorine, thallium or zinc, and the like. The excipient may be a conventional excipient, such as citric acid, malic acid, starch, etc., and other nutritional ingredients or other components may also be added.

 A calcium-containing composition of the present invention has the following formula (parts by weight): nano-calcium oxide 70-80

 Acid 4-6

 Malic acid 4-6

 Lake powder 3-5

 Sugar 3-5

 Trace elements 0.5-1 The trace elements in this formulation can be selected from one of magnesium, selenium, strontium, fluorine, iron or zinc or a mixture thereof. Bioactive animal bone density bioavailability test

Twenty Wister rats aged 1-2 months were randomly divided into three groups. The first group consisted of 6 rats. After feeding the ultrafine calcium oxide powder of the present invention, ^{6 of the} second group were fed with commercially available calcium carbonate, and ^{6 of the} third group were blank controls. The body weight was measured after 30 days. The results are shown in Table 1, and DPX-L from LUNAR was used. Dual energy; I: line bone density tester, measure its bone density (BMD), the results are shown in Table 2. The first group increased by 0.035g / cm ^{2 on} average, the second group increased by 0.027g / cm ^{2 on} average, and the third group increased by 0.014g / cm ^{2 on} average, which proves that the new type of nano calcium is easy for animals Absorbed by bones, bioavailability is 25% higher than calcium carbonate. Experimental weight change (g) of calcium oxide, calcium carbonate of the present invention and control rats (group) Group number Initial week, week, week, week, week, week, week, week

2 168 191 217 252 265 97

 No. 3 191 200 207 243 260 69

 1 4 177 190 197 234 265 88 80. 8 groups 12 185 195 200 237 260 75

 14 170 140 175 184 245 75

6 159 115 150 203 232 73

 No. 7 175 179 195 221 245 70

 2 8 178 167 188 221 250 72 68. 6 groups 9 167 173 198 223 236 69

 10 191 198 220 230 250 59 11th 194 197 219 241 256 62

Tue 13 195 200 192 221 207 12 38. 0 Group 5 161 161 111 145 201 40 Table 2 Changes in experimental bone mineral density (BMD g / cm ² ) of the calcium oxide, calcium carbonate, and control group of the present invention

Group No.Increment Number after 4 weeks

2 0.241 0.271 0 .030

 No. 3 0.245 0.274 0 '.029

 ― 4 0.247 0.271 0,, 024 0.035

 Group 12 0.249 0.279 0,, 030

 14 0.244 0.304 0,, 060

6 0.231 0.263 0. 032

 No. 7 0.246 0.288 0.04

 Tuesday 8 0.244 0.276 0. 032 0.027

 Group 9 0.242 0.253 0. 011

 10 0.247 0.266 0. 019 11th 0.250 0.278 0. 028

 Tuesday 13 0.264 0.275 0. 011 0.014

 Group 5 0.247 0.250 0.003

Test of absorption rate of calcium oxide of the present invention in rabbits

Two Japanese big-eared rabbits (age 3 months) were taken, and 2.5 g of calcium oxide of the present invention was administered to each, and the absorption rate of calcium in rabbits was measured by the "Ca radiotracer method", and rabbit No. 1 was measured It is 47.4% for rabbit No. 2 and 46.0% for rabbits, and it is about 30% for commercial calcium.

Table 3 "Ca distribution in rabbit No. 1 ■

 Spleen lung heart stomach

Sample sample name sample weight, g 'measured radioactivity unit weight radioactivity, count / 100S degrees, count / 100s «g

1-1 7.5 254 33.9 1-2 14 348 24.9 1-3 2.0 214 107

1-4 30.5 764 25.0

1-5 kidney + bladder 13.5 229 17.0

1-6 brain 6.5 201 30.9

1-7 Muscle 16 211 13.2

 1-8 liver 39.5 412 10.4

 -9 ear 26 383 14.7

 -10 colon 59.5 1873 31.5

 -11 Small intestine 76.5 1691 22.1

 -12 skull 3.0 1164 388

 -13 Upper limb bone 9.5 8631 909

 -14 Lower extremity bone 6.5 4299 661

-15 Blood 5.0 145 29 * Upper limb bones, lower limb bones, skull, ears, blood, muscles, and liver are all counted only partially, and the rest of the samples are almost all.

Table 4 Distribution of "Ca" in rabbit No. 2

 Sample sample name sample weight, g 'measured radioactivity unit weight radioactivity, count / 1Q0S degrees, count / lQGs, g

2-1 7.5 174 19 6

 2-2 7.0 215 30 7

2-3 2.0 174 87

2-4 40 743 18 6

 5 Kidney + Bladder 15 308 20.5

 6 brain 8.0 179 22.3

 7 muscle 8.5 262 30.8

 8 liver 49.5 551 113

 9 ears 17.5 168 9.6

 10 Colon 85.5 13042 153

 11 Small intestine 66.5 693 10.4

 12 skull 2.5 772 309

 13 Upper extremity bone 10.5 8988 856

 14 Lower extremity bone 19.0 18297 963

 15 blood 5 150 30

'The upper extremity bone, lower extremity bone, skull, ear, blood, muscle and liver were all counted only a few, and the rest of the samples were almost all, because the colon still had contents and the weight was high. Metabolic test of calcium oxide of the present invention in rabbits

 Two Japanese big-eared rabbits (aged 3 months) were infused with 2.5 g of calcium oxide of the present invention, and the "Ca distribution of the whole body of the rabbit was measured with a NZ8900 model camera. After 5 days, calcium had been deposited in the bones. It shows that calcium can be absorbed and utilized by rabbits.

 The following preferred examples illustrate the invention in detail, but do not limit the scope of the invention. Example 1

300 kg of calcium carbonate raw material with an average particle size of 100 meshes, sent from 1 atmosphere of air, etc. Ion reaction furnace (type PT1, produced by the Chemical and Metallurgical Institute of the Chinese Academy of Sciences) in which calcium carbonate raw materials are plasmaized by the energy from a plasma generator (type GP 100 -H, produced by the Institute of Mechanics of the Chinese Academy of Sciences) Decomposition occurred, and the temperature of the reaction furnace was 2500. (:. The reverse decomposition product was recovered by secondary bag filtration to obtain a white product with a yield of ⁵⁰ % (theoretical value of ⁵⁶ %). The carbon dioxide was discharged from the ventilator system. The particle size distribution curve of the white product was measured by X-ray diffraction. The results are shown in Figure 2. The average particle size of the product was about 10 ' ⁷ m. Example 2

The raw materials and operation procedures were the same as in Example 1, but the reaction temperature was controlled at 3000 ^e C, and the average particle size of the obtained product was less than 10 ·.

 Example 3: 70 kg of calcium oxide having a purity of 99.5% and an average particle diameter of 75 nanometers was added to a universal 120 liter mixer, and then 4 kg of citric acid, 4 kg of malic acid, and starch were added. 3 kilograms, 3 kilograms of sugar, 100 grams of strontium, 165 grams of fluorine, 150 grams of iron, and 170 grams of zinc were fully mixed and compressed into tablets in a general tablet machine, and the tablet weight was 0.5 grams, for a total of 165,000 tablets. The calcium-containing composition of the present invention is obtained.

 Example 4: except that the formula was changed to 80 kg of calcium oxide, 6 kg of citric acid, 6 kg of malic acid, 5 kg of starch, 5 kg of sugar and 120 g of strontium, 500 g of fluorine, 180 g of iron, and 130 g of zinc The remaining conditions were the same as in Example 3 to prepare the calcium-containing composition of the present invention.

Claims

Claim 1. An ultra-fine calcium oxide powder with a particle size of about 1C ^ -lCT ⁹ !! ^ 2. The calcium oxide powder according to claim 1, wherein the particles having a particle size of about 10 ' ⁶ -10 · account for more than 90%, 3. The calcium oxide powder according to claim 1, having a particle size of about 10 ' ⁷ -10' ⁸ m. 4. The calcium oxide powder according to claim ³ , wherein particles having a particle size of about 10 ' ⁷ -10'¾1 account for more than 70%, 5. An ultra-fine calcium oxide powder with an average particle size of about 10 '.  6. A calcium-containing composition for providing calcium to humans and / or animals, the composition comprising:  An ultra-fine calcium oxide powder with a particle size of about 10 '10',  One or more physiologically acceptable excipients and / or excipients. The calcium-containing composition of claim 6, wherein the particle size of the oxide is calcium powder 10 ^'7 -10'¾1. 8. The calcium-containing composition according to claim 6 or 7, wherein the calcium content accounts for more than 55%. 9. A product obtained by decomposing calcium carbonate by a plasma method, the particle size of the product is about 10 ·

10. The product of claim 9 having a particle size of about io ' ⁷ -io-V  11. A calcium-containing composition containing (parts by weight): nano-calcium oxide 70-80  Body acids 4-6  Malic acid 4-6  Lake powder 3-5  Sugar 3-5  Trace elements 0.5-1  12. Various calcium-rich foods, nutritional products, and medicines containing the ultra-fine calcium oxide powder according to claim 1 or 2.