CN108129292A - A kind of method that calcium acetate is prepared using ostreae testa pulverata - Google Patents
A kind of method that calcium acetate is prepared using ostreae testa pulverata Download PDFInfo
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- CN108129292A CN108129292A CN201810076763.2A CN201810076763A CN108129292A CN 108129292 A CN108129292 A CN 108129292A CN 201810076763 A CN201810076763 A CN 201810076763A CN 108129292 A CN108129292 A CN 108129292A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
Abstract
The present invention discloses a kind of method that calcium acetate is prepared using ostreae testa pulverata, and oyster shell is crushed, and sieves, and collects particle, coarse powder and fine powder respectively；Particle is calcined into obtain calcined oyster shell；Coarse powder plus boiling are boiled, the filtrate of filtering is concentrated to give oyster extract, and the aqueous oyster coarse powder for cleaning clean is added water after filter residue plus NaOH solution are handled, purified water, glacial acetic acid is added, is stirred to react to obtain calcium acetate reaction solution, through centrifuging to obtain clear supernatant；Calcined oyster shell adds water process to obtain calcined oyster shell suspension, adds gained supernatant, through filter cloth coarse filtration and micro porous filtration, obtains clear calcium acetate solution, add ethyl alcohol, squeezes and filter through strainer, and filter residue is through heated-air drying or is dried under reduced pressure to get to calcium acetate.The present invention is improved prepares the production efficiency of calcium acetate and finished product purity, and realize the recycling of ostreae testa pulverata using ostreae testa pulverata, while product quality is ensured, improves production efficiency, reduces energy consumption and cost.
Description
Technical field
The present invention relates to a kind of ostreae testa pulverata integrated conduct method more particularly to a kind of prepare calcium acetate using ostreae testa pulverata
Method belongs to medical manufacturing technology field.
Background technology
Oyster is commonly called as oyster, and the whole world has more than 100 kinds, and China has more than 20 kinds, is mainly distributed on coastal area.Now it is used as medicine
Oyster mainly has long oysterOstrea gigas Thunberg, ostrea talienwhanensis CrosseOstrea talienwhanensis
Crosse, Crassostrea rivularisOstrea rivularis Gould etc., shell are the major parts being used as medicine, have it is transquilization with heavy material,
Checking exuberance of yang tonifying yin, the function of softening and resolving hard mass, for insomnia of palpitating with fear, dizziness and tinnitus, scrofula subcutaneous nodule etc.；Calcined oyster shell convergence astringent method, relieving haperacidity
Analgesic, under spontaneous sweating, emission and spermatorrhea, uterine bleeding band, stomachache acid regurgitation etc..Contain a large amount of CaCO in oyster shell3, account for about male
The 95% of oyster shell weight is good natural calcium source.At present, there are calcium carbonate, vinegar by calcium preparation prepared by raw material of oyster shell both at home and abroad
Sour calcium, calcium propionate, calcium lactate, calcium citrate, calcium-glutamate chelate etc., develop and use it and are of great significance.
Calcium acetate is a kind of high efficiency nutritious hardening agent of ionic, has replenish the calcium superior performance, cheap, good absorption effect
The advantages that, solubility is 30~35%, is nearly 5000 times of raw oyster calcium.Human body is to calcium gluconate, calcium lactate, calcium carbonate
Absorption rate is respectively 27%, 32% and 38%, and the absorption rate of calcium acetate is up to 78%.In addition to calcium supplementing effect, calcium acetate
It clinically can be as the choice drug of hyperphosphatemia caused by treatment chronic renal failure.
About the preparation method of calcium acetate, the towering grade of model produces calcium acetate using direct method, and shell is investigated by experiment of single factor
The influence of powder diameter, acid adding amount, water, reaction time and pH Dichlorodiphenyl Acetates calcium content and yield, the results showed that, shell acid is than 0.75:
1st, water hull ratio is 21:1st, reaction time 140min, the content of calcium acetate and yield are up to 99.63%, 93.72% on this condition
（The such as Fan Zheng, Yang Xu, pass Jiaqing prepare food-level calcium acetate [J] food industry science and technology using discarded oyster shell as raw material
2015,10(36),254-258）.Wang Weibing etc. is that raw material prepares calcium acetate with eggshell, shows to work as vinegar by orthonormal design of experiments
Acid concentration is 9mol/L, a concentration of 2.5mol/L of NaOH solution a concentration of 4mol/L, HCL, reaction temperature are 50 DEG C, the reaction time
20min, calcium acetate yield is up to 65.62%（The such as Wang Weibing, Zhao Yueqiang, Sun Hong prepare the work of calcium acetate using egg shell as raw material
Skill research [J] Guangdong chemical industry 2015,42 (11)）.
In published patent of invention, " a kind of efficient calcium acetate preparation method "（CN106187742A）Disclose with
Calcium carbonate is raw material, and synthetic reaction is carried out, then filtered, be concentrated and dried preparation using ultrasonic constant-temperature magnetic agitation reactor
The method of calcium acetate, though the method accelerates the reaction time of whole preparation process, preparation process is complex, it is impossible to ensure raw material
Make full use of；In " a kind of production method of calcium acetate "（CN102643187A）In, with shell, glacial acetic acid, water at normal temperatures
More than 48h is stirred to react, produces calcium acetate raw material through processes such as coarse filtration, decoloration, refined filtration, dryings, the method technique is simple and direct, operational
By force, but the impurity effect by being brought in shell is unable to control, the calcium acetate raw material impurity content height of synthesis, product purity are relatively low；
At " using shell as the Calcium Ascorbate synthetic method of calcium source "（CN105732548A）In, by shell 0.05M salt acid soaks, powder
Broken and elutriation processing oyster shell whiting is proportionally added into ascorbic acid, oyster shell whiting and distilled water and carries out synthetic reaction, adds after suction filtration
Enter 95% ethyl alcohol to crystallize in -20 DEG C of refrigerators, 95% ethyl alcohol recrystallization, absolute ethyl alcohol is washed to get ascorbic acid calcium product, the method
Technical process is simple, but cannot remove inorganic impurity and fat in shell by pickling, and oyster shell whiting can not also carry out recycling profit
With；In " method that shell hydro-thermal process prepares high-purity calcite calcium carbonate micropowder "（CN103086414A）In, by oyster shell whiting
Broken sieving, is added in alkaline aqueous solution, is heat-treated in autoclave, is being detached, cleaned and is being dried to get high-purity
Calcite calcium carbonate micropowder is spent, the method technological operation is easy, and production efficiency is high, can clean the acid impurities and fat in oyster shell whiting
Ingredient still, is stayed in due to the part aqueous inorganic impurity in shell and alkaline reaction generation precipitation in finished product, it is impossible to reach
Remove the effect of inorganic impurity, also, because in cleaning process fine powder be difficult to realize detach with solution, processing time is longer, pair sets
Standby requirement is also high.
In conclusion the preparation method major part of current calcium acetate is that raw material uses directly using oyster shell whiting, calcium carbonate, egg shell
Connection is reacted with glacial acetic acid, it is contemplated that the cost of material of calcium carbonate especially precipitated calcium carbonate is higher, in the present invention, with resource
Oyster shell compared with horn of plenty is raw material, by multi-process integrated treatment, is used to prepare high-purity calcium acetate, has both made vinegar obtained by preparation
The calcareous amount of acid reaches domestic and international drug standards requirement, and can guarantee production efficiency, recycling that is cost-effective and realizing ostreae testa pulverata
It utilizes.
Invention content
The purpose of the present invention is to provide a kind of method that calcium acetate is prepared using ostreae testa pulverata, using pretreated oyster
Powder is raw material, and synthesis calcium acetate is reacted with glacial acetic acid, synthesis reaction solution is extracted obtain after purification more than 99% high-purity acetic acid
Calcium solves the problems such as acetic acid calcium content is low in the prior art, impurity is more, is provided for pharmaceutical industry and meets domestic and international standards of pharmacopoeia and want
The high-quality acetic acid calcium raw material drug asked.
To achieve these goals, the method for offer of the invention is as follows：It is a kind of to prepare vinegar using ostreae testa pulverata
The method of sour calcium, by following each step：
（1）Oyster shell is crushed, sieves, collects particle, 40~120 mesh coarse powder and 120 mesh screens more than 40 mesh screens respectively
Following fine powder；
（2）Step（1）It is middle class product of replenishing the calcium to be directly used in by the fine powder of 120 mesh screens；Take more than 40 mesh screens
Grain is placed in 800~1200 DEG C of 4~6h of calcining, obtains calcined oyster shell, cool down, be sealed, for use；
（3）Take step（1）In 40~120 mesh coarse powder, add in 3~5 times of quality purified water, boil 1~2h in stirring, filter
To filtrate and filter residue；Filtrate concentrates 10~20 times, obtains oyster extract；
（4）By step（3）In filter residue, add in 2~3 times of steps（1）A concentration of 0.5~1.0w/v%'s of gained meal quality
NaOH solution boils 0.5~1h in stirring, solution is abandoned in filtering；Filter residue is with 3~5 times of steps（1）The purifying of gained meal quality
It is cleaned 2~3 times in water stirring, until cleaning solution pH=6~8, abandon water layer, obtain clean aqueous oyster coarse powder；
（5）Clean aqueous oyster coarse powder is taken, conventionally, adds in 3~4 times of steps（1）The purifying of gained meal quality
Water is slowly added to 1~2 times of step in stirring（1）The glacial acetic acid of gained meal quality, is stirred to react 24~36h, and it is anti-to obtain calcium acetate
Answer liquid；
（6）Calcium acetate reaction solution is taken to be centrifuged with 8000~10000rpm, obtains clear supernatant；Precipitation is collected, with taking step（3）
Obtained oyster extract merges, and resourcebility is used to prepare oyster hydrolysate；
（7）Take step（2）Gained calcined oyster shell, the purified water of 3~5 times of calcined oyster shell quality of addition, 0.5~1h of stirring, standing 2~
3h abandons supernatant；Precipitation adds in the purified water of 2~3 times of calcined oyster shell quality, stirs evenly, obtains calcined oyster shell suspension；
（8）Take step（7）Gained calcined oyster shell suspension, step is added in stirring（6）Gained supernatant, until pH is 6~8,
Through 200 mesh filter cloth coarse filtration and 1um micro porous filtrations, clear calcium acetate solution is obtained；
（9）Take step（8）Gained calcium acetate solution adds in a concentration of 95v/v% ethyl alcohol of 2~5 times of calcium acetate solution volumes, warp
200 mesh are squeezed with upper filter screen and filtered, decompression filtrate recycling ethanol；Filter residue through 60~75 DEG C of heated-air dryings or be dried under reduced pressure to get
To the calcium acetate of more than 99.0% purity.
The step（1）Oyster shell meet current edition《Chinese Pharmacopoeia》The oyster shell of standard.
Advantages of the present invention and effect are：The present invention provides the effective ways of ostreae testa pulverata comprehensive utilization, by oyster shell
The ostreae testa pulverata for different-grain diameter is crushed and screened, is respectively processed, improves production efficiency, reduces the wasting of resources, realizes ostreae testa pulverata
Recycling.
（1）It is sieved after oyster shell is crushed, the fine powder below 120 mesh screens takes orally easy absorption, is used directly for mending
Calcium product.It is difficult during water extraction below and alkali process because particle is too thin if being mixed for preparing calcium acetate with coarse powder
To realize the good separation of powder and solution, filter efficiency is influenced.
（2）40~120 mesh oyster coarse powder, through boiling boil extract, removal wherein amino acid, polysaccharide, sodium salt, sylvite, magnesium salts,
The water-soluble substances such as molysite, zinc salt, aluminium salt, sulfate, nitrate, chloride；Again through base extraction, part egg therein is removed
The organic substances such as white matter, fat, are rinsed well lye with water, so as to achieve the purpose that purify ostreae testa pulverata.If do not first pass through water
It extracts directly using base extraction, the metal salts such as magnesium, iron, zinc, aluminium and alkali react, and generate precipitation, it is impossible to realize and remove
The purpose of impurity.
（3）Oyster particles more than 40 mesh screens, water extraction and alkali process can only remove the impurity of particle surface, it is difficult to reach
To expected clean-up effect, and because particle is too big, reduce the efficiency reacted with glacial acetic acid and prepare calcium acetate.Therefore, using forging
The method of burning improves reactivity, can not only make full use of resource, but also can improve production efficiency；Also, in calcination process, greatly
Partial organic substances are decomposed, and in water-washing process below, debris and soluble inorganic impurity can remove completely,
So as to achieve the purpose that reduce impurity content.
（4）It is reacted using ostreae testa pulverata with glacial acetic acid and prepares calcium acetate, contained ingredients calcium carbonate can react substantially in oyster
It completely and is dissolved in reaction solution, the nutritional ingredients such as remaining partially protein, polysaccharide can be collected by filtration, and institute is extracted with water
Oyster extract merges, realize and carry out recycling, can be used for preparing the relatively low oyster hydrolysate of inorganic salt content or
It is directly used in nutraceutical.
（5）Because calcium acetate is insoluble in ethyl alcohol, filtered clear calcium acetate solution after adding in ethyl alcohol, can form gel
Precipitation is difficult to realize separation of solid and liquid using filtering or centrifugation, and after squeezing and filtering, the part alcohol in calcium acetate solution is molten
Property organic and inorganic impurity stay in the solution, it is reusable after ethyl alcohol is recovered；The relatively low calcium acetate gel of water content is collected,
After drying, you can obtain the calcium acetate of more than 99.0% purity.
Compared with conventional method, the present invention is improved prepares the production efficiency of calcium acetate and finished product purity using ostreae testa pulverata,
And the recycling of ostreae testa pulverata is realized, while product quality is ensured, production efficiency is improved, reduces energy consumption and cost.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
（1）Selection meets current edition《Chinese Pharmacopoeia》The oyster shell 50kg of standard, oyster shell is crushed, and screening collects 40 respectively
The fine powder below particle, 40~120 mesh coarse powder and 120 mesh screens more than mesh screen；
（2）Step（1）It is middle class product of replenishing the calcium to be directly used in by the fine powder of 120 mesh screens；Take more than 40 mesh screens
Grain is placed in 900 DEG C of calcining 5h, obtains calcined oyster shell, cool down, be sealed, for use；
（3）Take step（1）In 40~120 mesh coarse powder, add in 4 times of quality purified water, boil 1h in stirring, filtrate be obtained by filtration
And filter residue；Filtrate concentrates 15 times, obtains oyster extract；
（4）By step（3）In filter residue, add in 2 times of steps（1）The NaOH solution of a concentration of 1.0w/v% of gained meal quality,
1h is boiled in stirring, filters, abandons solution；Filter residue is with 4 times of steps（1）2~3 are cleaned in the purified water stirring of gained meal quality
It is secondary, until cleaning solution pH=6~8, abandon water layer, obtain clean aqueous oyster coarse powder；
（5）Clean aqueous oyster coarse powder is taken, conventionally, adds in 3 times of steps（1）The purified water of gained meal quality,
2 times of steps are slowly added in stirring（1）The glacial acetic acid of gained meal quality, is stirred to react 30h, obtains calcium acetate reaction solution；
（6）Calcium acetate reaction solution is taken to be centrifuged with 9000rpm, obtains clear supernatant；Precipitation is collected, with taking step（3）It obtains
Oyster extract merges, and resourcebility is used to prepare oyster hydrolysate；
（7）Take step（2）Gained calcined oyster shell adds in the purified water of 4 times of calcined oyster shell quality, stirs 1h, stands 2h, abandons supernatant；
Precipitation adds in the purified water of 3 times of calcined oyster shell quality, stirs evenly, obtains calcined oyster shell suspension；
（8）Take step（7）Gained calcined oyster shell suspension, step is added in stirring（6）Gained supernatant, until pH is 6~8,
Through 200 mesh filter cloth coarse filtration and 1um micro porous filtrations, clear calcium acetate solution is obtained；
（9）Take step（8）Gained calcium acetate solution adds in a concentration of 95v/v% ethyl alcohol of 4 times of calcium acetate solution volumes, through 200
Mesh is squeezed with upper filter screen and filtered, decompression filtrate recycling ethanol；Filter residue is through 70 DEG C of heated-air dryings or is dried under reduced pressure to get to purity
More than 99.0% calcium acetate.
Embodiment 2
（1）Selection meets current edition《Chinese Pharmacopoeia》The oyster shell 70kg of standard, oyster shell is crushed, and screening collects 40 respectively
The fine powder below particle, 40~120 mesh coarse powder and 120 mesh screens more than mesh screen；
（2）Step（1）It is middle class product of replenishing the calcium to be directly used in by the fine powder of 120 mesh screens；Take more than 40 mesh screens
Grain is placed in 1100 DEG C of calcining 4h, obtains calcined oyster shell, cool down, be sealed, for use；
（3）Take step（1）In 40~120 mesh coarse powder, add in 3 times of quality purified water, boil 2h in stirring, filtrate be obtained by filtration
And filter residue；Filtrate concentrates 10 times, obtains oyster extract；
（4）By step（3）In filter residue, add in 3 times of steps（1）The NaOH solution of a concentration of 0.5w/v% of gained meal quality,
0.5h is boiled in stirring, filters, abandons solution；Filter residue is with 3 times of steps（1）2~3 are cleaned in the purified water stirring of gained meal quality
It is secondary, until cleaning solution pH=6~8, abandon water layer, obtain clean aqueous oyster coarse powder；
（5）Clean aqueous oyster coarse powder is taken, conventionally, adds in 3 times of steps（1）The purified water of gained meal quality,
1 times of step is slowly added in stirring（1）The glacial acetic acid of gained meal quality is stirred to react for 24 hours, obtains calcium acetate reaction solution；
（6）Calcium acetate reaction solution is taken to be centrifuged with 8000rpm, obtains clear supernatant；Precipitation is collected, with taking step（3）It obtains
Oyster extract merges, and resourcebility is used to prepare oyster hydrolysate；
（7）Take step（2）Gained calcined oyster shell adds in the purified water of 3 times of calcined oyster shell quality, stirs 0.5h, stands 2h, abandons supernatant
Liquid；Precipitation adds in the purified water of 2 times of calcined oyster shell quality, stirs evenly, obtains calcined oyster shell suspension；
（8）Take step（7）Gained calcined oyster shell suspension, step is added in stirring（6）Gained supernatant, until pH is 6~8,
Through 200 mesh filter cloth coarse filtration and 1um micro porous filtrations, clear calcium acetate solution is obtained；
（9）Take step（8）Gained calcium acetate solution adds in a concentration of 95v/v% ethyl alcohol of 2 times of calcium acetate solution volumes, through 200
Mesh is squeezed with upper filter screen and filtered, decompression filtrate recycling ethanol；Filter residue is through 60 DEG C of heated-air dryings or is dried under reduced pressure to get to purity
More than 99.0% calcium acetate.
Embodiment 3
（1）Selection meets current edition《Chinese Pharmacopoeia》The oyster shell 100kg of standard, oyster shell is crushed, and screening collects 40 respectively
The fine powder below particle, 40~120 mesh coarse powder and 120 mesh screens more than mesh screen；
（2）Step（1）It is middle class product of replenishing the calcium to be directly used in by the fine powder of 120 mesh screens；Take more than 40 mesh screens
Grain is placed in 800 DEG C of calcining 6h, obtains calcined oyster shell, cool down, be sealed, for use；
（3）Take step（1）In 40~120 mesh coarse powder, add in 5 times of quality purified water, boil 2h in stirring, filtrate be obtained by filtration
And filter residue；Filtrate concentrates 20 times, obtains oyster extract；
（4）By step（3）In filter residue, add in 3 times of steps（1）The NaOH solution of a concentration of 0.8w/v% of gained meal quality,
0.8h is boiled in stirring, filters, abandons solution；Filter residue is with 5 times of steps（1）2~3 are cleaned in the purified water stirring of gained meal quality
It is secondary, until cleaning solution pH=6~8, abandon water layer, obtain clean aqueous oyster coarse powder；
（5）Clean aqueous oyster coarse powder is taken, conventionally, adds in 4 times of steps（1）The purified water of gained meal quality,
2 times of steps are slowly added in stirring（1）The glacial acetic acid of gained meal quality, is stirred to react 36h, obtains calcium acetate reaction solution；
（6）Calcium acetate reaction solution is taken to be centrifuged with 10000rpm, obtains clear supernatant；Precipitation is collected, with taking step（3）It obtains
Oyster extract merges, and resourcebility is used to prepare oyster hydrolysate；
（7）Take step（2）Gained calcined oyster shell adds in the purified water of 5 times of calcined oyster shell quality, stirs 0.8h, stands 3h, abandons supernatant
Liquid；Precipitation adds in the purified water of 3 times of calcined oyster shell quality, stirs evenly, obtains calcined oyster shell suspension；
（8）Take step（7）Gained calcined oyster shell suspension, step is added in stirring（6）Gained supernatant, until pH is 6~8,
Through 200 mesh filter cloth coarse filtration and 1um micro porous filtrations, clear calcium acetate solution is obtained；
（9）Take step（8）Gained calcium acetate solution adds in a concentration of 95v/v% ethyl alcohol of 5 times of calcium acetate solution volumes, through 200
Mesh is squeezed with upper filter screen and filtered, decompression filtrate recycling ethanol；Filter residue is through 70 DEG C of heated-air dryings or is dried under reduced pressure to get to purity
More than 99.0% calcium acetate.
Embodiment 4
（1）Selection meets current edition《Chinese Pharmacopoeia》The oyster shell 80kg of standard, oyster shell is crushed, and screening collects 40 respectively
The fine powder below particle, 40~120 mesh coarse powder and 120 mesh screens more than mesh screen；
（2）Step（1）It is middle class product of replenishing the calcium to be directly used in by the fine powder of 120 mesh screens；Take more than 40 mesh screens
Grain is placed in 1200 DEG C of calcining 4h, obtains calcined oyster shell, cool down, be sealed, for use；
（3）Take step（1）In 40~120 mesh coarse powder, add in 5 times of quality purified water, boil 2h in stirring, filtrate be obtained by filtration
And filter residue；Filtrate concentrates 16 times, obtains oyster extract；
（4）By step（3）In filter residue, add in 3 times of steps（1）The NaOH solution of a concentration of 0.5w/v% of gained meal quality,
1h is boiled in stirring, filters, abandons solution；Filter residue is with 3~5 times of steps（1）Gained meal quality purified water stirring in cleaning 2~
3 times, until cleaning solution pH=6~8, abandon water layer, obtain clean aqueous oyster coarse powder；
（5）Clean aqueous oyster coarse powder is taken, conventionally, adds in 4 times of steps（1）The purified water of gained meal quality,
1 times of step is slowly added in stirring（1）The glacial acetic acid of gained meal quality, is stirred to react 24~36h, obtains calcium acetate reaction solution；
（6）Calcium acetate reaction solution is taken to be centrifuged with 8000rpm, obtains clear supernatant；Precipitation is collected, with taking step（3）It obtains
Oyster extract merges, and resourcebility is used to prepare oyster hydrolysate；
（7）Take step（2）Gained calcined oyster shell adds in the purified water of 3 times of calcined oyster shell quality, stirs 1h, stands 3h, abandons supernatant；
Precipitation adds in the purified water of 3 times of calcined oyster shell quality, stirs evenly, obtains calcined oyster shell suspension；
（8）Take step（7）Gained calcined oyster shell suspension, step is added in stirring（6）Gained supernatant, until pH is 6~8,
Through 200 mesh filter cloth coarse filtration and 1um micro porous filtrations, clear calcium acetate solution is obtained；
（9）Take step（8）Gained calcium acetate solution adds in a concentration of 95v/v% ethyl alcohol of 2 times of calcium acetate solution volumes, through 200
Mesh is squeezed with upper filter screen and filtered, decompression filtrate recycling ethanol；Filter residue is through 75 DEG C of heated-air dryings or is dried under reduced pressure to get to purity
More than 99.0% calcium acetate.
Using United States Pharmacopeia USP40 methods, prepare gained sample to the embodiment of the present invention 1~4 and commercial product be detected and
Comparative analysis.It is as follows to predominantly detect method：
（1）Acid-base value：5% sample solution is prepared, pH value of solution is measured according to pH inspection techniques, should be 6.3~9.6.
（2）Content：Sample 300mg is weighed, is dissolved in the 150ml water of the 2ml of hydrochloric acid containing 3mol/L, under agitation,
The EDTA titrating solutions about 30ml of 0.05mol/L is added in from 50ml burets, adds in 1mol/L sodium hydroxide solutions 15ml and hydroxyl
Base naphthol blue 300mg, and continue to be titrated to solution and show blue, the EDTA titrating solutions per 1ml are equivalent to the calcium acetate of 7.909mg,
Acetic acid calcium content should be 99.0%~100.5% in product（In terms of anhydride）.
（3）Chloride：Sample 1.0g is weighed, according to chloride inspection technique, contained chloride must not exceed correspondence
Amount contained by 0.7ml, 0.020mol/L hydrochloric acid solution（0.05%）.
（4）Sulfate：Sample 0.25g is weighed, according to sulfate inspection technique, contained sulfate must not exceed correspondence
Amount contained by the sulfuric acid solution of 0.15ml, 0.040mol/L（0.06%）.
（5）Magnesium salts
A. standard solution is prepared：It takes magnesia appropriate, is dissolved in 1mol/L salpeter solutions, be configured to the magnesium elements of 1000 μ g/ml
Standard Stock solutions.Before use, stock solution is taken to be diluted to the magnesium standard solution of 5 μ g/ml.
B. sample solution is prepared：It takes calcium acetate sample appropriate, is dissolved in water and is made the calcium acetate solution of 2mg/ml.
C. linear criterion solution A is prepared：Precision measures sample solution 20.0ml, water is added to be settled to 25.0ml, as 0 μ g/
The magnesium standard solution of ml.
D. linear criterion solution B is prepared：Precision measures standard solution 2.0ml and sample solution 20.0ml, and water is added to be settled to
25.0ml, the magnesium standard solution as 0.4 μ g/ml.
E. linear criterion solution C is prepared：Precision measures standard solution 4.0ml and sample solution 20.0ml, and water is added to be settled to
25.0ml, the magnesium standard solution as 0.8 μ g/ml.
F. atomic absorption spectrography (AAS) testing conditions：Wavelength 258.2nm, Air-acetylene Flame are analyzed, element lamp is magnesium sky
Heart cathode modulation, water are blank.
G. analytical procedure：Using linear criterion solution A, the absorbance of B, C as abscissa, corresponding concentration（0th, 0.4 and
The magnesium density of 0.8 μ g/ml）For ordinate, by three point-rendering matched curves, and straight line of extrapolating intersects with abscissa, from intercept
Read the content of magnesium elements in sample solution（In terms of μ g/mL）, which is multiplied by the percentage composition of magnesium in 0.0625 calculating sample,
Content of magnesium must not exceed 0.05% in sample.
（6）Sodium salt
A. standard solution is prepared：The sodium chloride of the dry 2h at 105 DEG C in advance is taken, is formulated as 25.42mg/mL solution, as phase
When in the sodium standard reserving solution of 10.0mg/mL.Before use, stock solution is taken to be diluted to the sodium standard solution of 250 μ g/mL.
B. sample solution is prepared：It takes calcium acetate sample appropriate, is dissolved in water and is formulated as the calcium acetate solution of 10mg/ml.
C. linear criterion solution A is prepared：Precision measures sample solution 20.0ml, water is added to be settled to 25.0ml, as 0 μ g/
The sodium standard solution of ml.
D. linear criterion solution B is prepared：Precision measures standard solution 2.0ml and sample solution 20.0ml, and water is added to be settled to
25.0ml, the sodium standard solution as 20 μ g/ml.
E. linear criterion solution C is prepared：Precision measures standard solution 4.0ml and sample solution 20.0ml, and water is added to be settled to
25.0ml, the sodium standard solution as 40 μ g/ml.
F. atomic absorption spectrography (AAS) testing conditions：Wavelength 589.0nm, Air-acetylene Flame are analyzed, element lamp is sodium sky
Heart cathode modulation, water are blank.
G. analytical procedure：Using linear criterion solution A, the absorbance of B, C as abscissa, corresponding concentration（0th, 20 and 40
The na concn of μ g/ml）For ordinate, by three point-rendering matched curves, and straight line of extrapolating intersects with abscissa, is read from intercept
The amount of sodium element in sample solution（In terms of μ g/mL）, by the way that the value to be multiplied by the percentage composition of sodium in 0.0125 calculating sample, sample
Sodium content must not exceed 0.5% in product.
By being detected to the analysis of sample the key technical indexes acid-base value, content, chloride, sulfate, magnesium salts, sodium salt,
Compared with commercial product, product purity prepared by the present invention reaches more than 99%, and other impurities limitation also complies with United States Pharmacopeia
The requirement of USP40 respective standards, testing result are shown in Table -1.
- 1 acetic acid calcium product the key technical indexes of table detects
。
Claims (2)
- A kind of 1. method that calcium acetate is prepared using ostreae testa pulverata, it is characterised in that pass through following each step：（1）Oyster shell is crushed, sieves, collects particle, 40~120 mesh coarse powder and 120 mesh screens more than 40 mesh screens respectively Following fine powder；（2）Particles more than 40 mesh screens is taken, 800~1200 DEG C of 4~6h of calcining is placed in, obtains calcined oyster shell, cool down, be sealed, For use；（3）Take step（1）In 40~120 mesh coarse powder, add in 3~5 times of quality purified water, boil 1~2h in stirring, filter To filtrate and filter residue；Filtrate concentrates 10~20 times, obtains oyster extract；（4）By step（3）In filter residue, add in 2~3 times of steps（1）A concentration of 0.5~1.0w/v%'s of gained meal quality NaOH solution boils 0.5~1h in stirring, solution is abandoned in filtering；Filter residue is with 3~5 times of steps（1）The purifying of gained meal quality It is cleaned 2~3 times in water stirring, until cleaning solution pH=6~8, abandon water layer, obtain clean aqueous oyster coarse powder；（5）Clean aqueous oyster coarse powder is taken, conventionally, adds in 3~4 times of steps（1）The purifying of gained meal quality Water is slowly added to 1~2 times of step in stirring（1）The glacial acetic acid of gained meal quality, is stirred to react 24~36h, and it is anti-to obtain calcium acetate Answer liquid；（6）Calcium acetate reaction solution is taken to be centrifuged with 8000~10000rpm, obtains clear supernatant；（7）Take step（2）Gained calcined oyster shell, the purified water of 3~5 times of calcined oyster shell quality of addition, 0.5~1h of stirring, standing 2~ 3h abandons supernatant；Precipitation adds in the purified water of 2~3 times of calcined oyster shell quality, stirs evenly, obtains calcined oyster shell suspension；（8）Take step（7）Gained calcined oyster shell suspension, step is added in stirring（6）Gained supernatant, until pH is 6~8, Through 200 mesh filter cloth coarse filtration and 1um micro porous filtrations, clear calcium acetate solution is obtained；（9）Take step（8）Gained calcium acetate solution adds in a concentration of 95v/v% ethyl alcohol of 2~5 times of calcium acetate solution volumes, warp 200 mesh are squeezed with upper filter screen and filtered, decompression filtrate recycling ethanol；Filter residue through 60~75 DEG C of heated-air dryings or be dried under reduced pressure to get To calcium acetate.
- 2. the method according to claim 1 that calcium acetate is prepared using ostreae testa pulverata, it is characterised in that：The step（1）'s Oyster shell meets《Chinese Pharmacopoeia》The oyster shell of standard.
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