CN102838477A - Method for preparing high-purity calcium lactate by taking oyster shell as raw material - Google Patents

Abstract

The invention discloses a method for preparing high-purity calcium lactate by taking oyster shell as raw material. The method comprises the following steps: treating oyster shells through a water-refining method, converting the oyster shell with lactic acid, adding precipitator, flocculant and a decolorizing agent, and crystallizing to obtain high-purity calcium lactate. The obtained calcium lactate has high content, and is white in color, low in heavy metal residue and high in product yield.

Description

With the oyster shells is the method for feedstock production high-pure lactic acid calcium

Technical field

The present invention relates to a kind of preparation method of lactic acid ca, particularly a kind of is the method for feedstock production high-pure lactic acid calcium with the oyster shells.

Background technology

Crassostrea rivularis has another name called big oyster, is one of Qiezhou, Guangxi four big famous and precious marine products, and meat can be eaten raw, also can be processed into dried oyster, oyster sauce.Big oyster oyster meat is the fishery products with very high nutrition and health care function of protein-high, lower fat, delicious flavour, and oyster meat protein content surpasses 40%, and is nutritious, and delicious flavour have the title of " marine milk ", also can be used as medicine simultaneously.Big oyster meat is rich in taurine, can promote the human brain development.

In recent years, oyster has become the important marine products economic shellfish output of China and has constantly increased, and is discarded in the refuse tip mostly or fills out the sea as solid waste and account for the oyster shells of its gross weight more than 80%, has become environment one big public hazards.The Chinese medicine oyster is the shell of Ostreidae animal Crassostrea rivularis, long oyster, Dalian Bay Concha Ostreae etc., because wherein the content of lime carbonate is feedstock production biological calcium paid more and more attention up to about 90% with the oyster shell.But, according to bibliographical information, because how in the form of sheets or the strip form agent structure of shell; Internal void is bigger; The connectedness in hole is better, and fluid is easy to be diffused into along the passage of bar shaped the surface of laminated structure, thereby coating interior is led in infiltration; Thereby shell possessed the essential characteristic of sorbent material, and the heavy metal in the seawater is had absorption property.Therefore, bivalve (especially mussel and oyster) has very strong accumulation ability to heavy metal, can be used as the biological indicator species of pollution of the sea, and there is positive correlation in its heavy metal of body concentration (especially Pb) with marine environment.At present, the production technique of shell biological calcium is to be raw material with the oyster shell mostly, after washing, calcines or does not calcine and directly extract conversion, and the Pb massfraction is up to 3x10 in its product ^-5-10x10 ^-5, be higher than far away that the Pb massfraction is lower than 1.5x10 in the medicinal organism calcium of Bureau of Drugs Supervision promulgation ^-5Requirement.And because the oyster shell place of production is different, its heavy metal content differs greatly, and causes quality product to can not get good guarantee.Particularly in recent years, because offshore pollution, it is a ubiquitous problem that the biological calcium product lead that is obtained by the oyster shell roasting exceeds standard.

Along with going from strength to strength of oyster culture industry, the oyster shells resource becomes increasingly abundant, and the oyster deep processing is the only way which must be passed that industry enlarges development.At present, the supplementary calcium food of clinical application and calcic type of preparation are a lot, and shell in the main source Yu Haiyang and bright bone mainly comprise organic calciums such as lactic acid ca, calglucon, citrate of lime.Wherein, Because characteristics such as lactic acid ca has the solubleness height, bioavailability is high, mouthfeel is good, calcium contents height; Creta Preparata, glue crosslinking agent, solidifying agent be can be widely used in and crisp dose and toothpaste, cigarette quality modifying agent increased; Especially as medicine and protective foods, more need highly purified lactic acid ca.

In the prior art, make the lactic acid ca that meets the pharmacopeia requirement and pass through secondary crystal even repeatedly crystallization more, but loss is too big, every crystallization once loses 10%; With edible lactic acid and the reaction of medicinal lactic acid ca, also can make qualified medicinal lactic acid ca, but capital is too high.Therefore, develop a kind of method that can effectively reduce oyster shell biological calcium product P b content, the preparation method of technical maturity, simple high-pure lactic acid calcium is the practical problems that needs to be resolved hurrily at present.

Summary of the invention

What the invention provides that a kind of technology is simple, efficient is high is the working method of feedstock production high-pure lactic acid calcium with the oyster shells.

The present invention realizes through following technical scheme:

A kind of is the method for feedstock production high-pure lactic acid calcium with the oyster shells, comprises the steps:

A. oyster shells is scrubbed clean, dries, be crushed to granularity with ball mill and get the oyster shells meal at the 80-100 order;

B. with the above-mentioned oyster shells meal that obtains, put in the appropriate vessel, add proper amount of clear water; Grind to form pasty state, the water that adds volume again stirs, and inclining immediately suspension; Carry out repeatedly so repeatedly, impurity that can not suspendible discards, and the suspension that treating repeatedly inclines leaves standstill, post precipitation; Inclining top clear water, will drain throw out and be used for following steps;

C. in 50-60 ℃ of heating in water bath, constantly stir, slowly add weight in the above-mentioned oyster shell powder that obtains and be the heavy 2.0-2.5 of coarse grist doubly and concentration be the lactic acid solution of 75-85%, total reaction time is 2-5 hour;

D. above-mentioned gained suspension is filtered, in filtrating, add precipitation agent sal epsom, add-on left standstill 2-3 hour for the 0.20-0.25% of filtrating quality;

E. will go up step gained suspension and filter, adjustment filtrating pH is 9-10, in filtrating, adds the flocculation agent SEPIGEL 305, and add-on is the 0.0010-0.0015% of the quality of filtrating, temperature of reaction 80-90 ℃, kept 0.5-1 hour;

F. will go up step gained suspension and filter, add the discoloring agent 30% concentration H of the quality 0.001-0.002% that is equivalent to filtrate ₂O ₂, stir, leave standstill crystallization in 12-18 hour, filter;

G. with above-mentioned gained crystallization 95-100 ℃ of drying, promptly get white lactic acid ca.

The lactic acid ca that adopts the inventive method to make, color and luster is pure white, and product purity reaches more than 99%, and heavy metal lead remains in below the 0.1ppm.

Compared with prior art, advantage of the present invention:

1, through to the impurity composition analysis, in technology, add efficient precipitation agent, flocculation agent and discoloring agent, impurity such as protein-based, lipid, starch fine particle are fully removed, it is as clear as crystal to guarantee to filtrate, and primary crystallization just makes product reach the pharmacopeia requirement like this;

2, the present invention only adopts primary crystallization, compares twice or above recrystallization, and the yield of product improves more than 10%, and the whole process time also shortens greatly.

Embodiment

With embodiment the present invention is described further below, but the present invention is not limited to these embodiment.

Embodiment 1:

A kind of is the method for feedstock production high-pure lactic acid calcium with the oyster shells, comprises the steps:

A. oyster shells is scrubbed clean, dries, be crushed to granularity with ball mill and get the oyster shells meal at 80 orders;

B. with the above-mentioned oyster shells meal 1kg that obtains, put in the stainless steel cask, add proper amount of clear water; Grind to form pasty state, the water that adds volume again stirs, and inclining immediately suspension; Carry out repeatedly so repeatedly, impurity that can not suspendible discards, and the suspension that treating repeatedly inclines leaves standstill, post precipitation; Inclining top clear water, will drain throw out and be used for following steps;

C. in 50 ℃ of heating in water bath, constantly stir, slowly add concentration in the above-mentioned oyster shell powder that obtains and be 75% lactic acid solution 2.5kg, total reaction time is 3 hours;

D. above-mentioned gained suspension is filtered, in filtrating, add precipitation agent sal epsom 6.5g, left standstill 3 hours;

E. will go up step gained suspension and filter, adjustment filtrating pH is 10, adding flocculation agent SEPIGEL 305 0.03g in the filtrating, temperature of reaction 80-90 ℃, kept 1 hour;

F. will go up step gained suspension and filter, add the discoloring agent 30% concentration H of 0.03g ₂O ₂, stir, leave standstill crystallization in 18 hours, filter;

G. with above-mentioned gained crystallization 100 ℃ of dryings, promptly get purity 99.6%, lead content is the white lactic acid ca 1.72kg of 0.05ppm.

Embodiment 2:

A kind of is the method for feedstock production high-pure lactic acid calcium with the oyster shells, comprises the steps:

A. oyster shells is scrubbed clean, dries, be crushed to granularity with ball mill and get the oyster shells meal at 100 orders;

B. with the above-mentioned oyster shells meal 1kg that obtains, put in the stainless steel cask, add proper amount of clear water; Grind to form pasty state, the water that adds volume again stirs, and inclining immediately suspension; Carry out repeatedly so repeatedly, impurity that can not suspendible discards, and the suspension that treating repeatedly inclines leaves standstill, post precipitation; Inclining top clear water, will drain throw out and be used for following steps;

C. in 60 ℃ of heating in water bath, constantly stir, slowly add concentration in the above-mentioned oyster shell powder that obtains and be 75% lactic acid solution 2.0kg, total reaction time is 5 hours;

D. above-mentioned gained suspension is filtered, in filtrating, add precipitation agent sal epsom 8.25g, left standstill 2 hours;

E. will go up step gained suspension and filter, adjustment filtrating pH is 9, adding flocculation agent SEPIGEL 305 0.05g in the filtrating, temperature of reaction 80-90 ℃, kept 1 hour;

F. will go up step gained suspension and filter, add the discoloring agent 30% concentration H of 0.06g ₂O ₂, stir, leave standstill crystallization in 12 hours, filter;

G. with above-mentioned gained crystallization 100 ℃ of dryings, promptly get purity 99.7%, lead content is the white lactic acid ca 1.75kg of 0.06ppm.

Claims (1)

1. one kind is the method for feedstock production high-pure lactic acid calcium with the oyster shells, comprises the steps:

A. oyster shells is scrubbed clean, dries, be crushed to granularity with ball mill and get the oyster shells meal at the 80-100 order;

B. with the above-mentioned oyster shells meal that obtains, put in the appropriate vessel, add proper amount of clear water; Grind to form pasty state, the water that adds volume again stirs, and inclining immediately suspension; Carry out repeatedly so repeatedly, impurity that can not suspendible discards, and the suspension that treating repeatedly inclines leaves standstill, post precipitation; Inclining top clear water, will drain throw out and be used for following steps;

C. in 50-60 ℃ of heating in water bath, constantly stir, slowly add weight in the above-mentioned oyster shell powder that obtains and be the heavy 2.0-2.5 of coarse grist doubly and concentration be the lactic acid solution of 75-85%, total reaction time is 2-5 hour;

D. above-mentioned gained suspension is filtered, in filtrating, add precipitation agent sal epsom, add-on left standstill 2-3 hour for the 0.20-0.25% of filtrating quality;

E. will go up step gained suspension and filter, adjustment filtrating pH is 9-10, in filtrating, adds the flocculation agent SEPIGEL 305, and add-on is the 0.0010-0.0015% of the quality of filtrating, temperature of reaction 80-90 ℃, kept 0.5-1 hour;

F. will go up step gained suspension and filter, add the discoloring agent 30% concentration H of the quality 0.001-0.002% that is equivalent to filtrate ₂O ₂, stir, leave standstill crystallization in 12-18 hour, filter;

G. with above-mentioned gained crystallization 95-100 ° of C drying, promptly get white lactic acid ca.