CN101016239A - Method of extracting calcium gluconate from mother liquid after calcium gluconate crystallization - Google Patents

Abstract

The invention discloses an extracting method of calcium gluconate from mother liquid of fermented calcium gluconate crystal, which comprises the following steps: 1. removing impurity through active charcoal; 2. condensing at 100 deg.c; cooling; 3. crystallizes after blending alcohol evenly; 4. pouring supernatant; sucking; washing crystal through anhydrous alcohol.

Description

After the calglucon crystallization, extract the method for calglucon the mother liquor

Technical field

The present invention relates to a kind of method of after the calglucon crystallization, extracting calglucon the mother liquor.

Background technology

Calglucon (calcium gluconate) is the calcium salt of gluconic acid, and molecular formula is C ₁₂H ₂₂CaO ₁₄H ₂O, molecular weight are 448.40, and 201 ℃ of fusing points are white crystals shape or powder, and odorless, tasteless is dissolved in cold water, is soluble in hot water, is insoluble to dehydrated alcohol, chloroform or ether.Calglucon is a kind of important organic calcium, clinically as the supplement of calcium, also is the raw material of producing other gluconates (Zinc Gluconate, ferrous gluconate etc.) and gluconic acid delta-lactone, is China's important chemical exported product.

The method for preparing calglucon mainly contains chemical method and fermentation method, and wherein the fermentation method technical process is:

(1) saccharification: with starch, rice, flour or Semen Maydis powder is raw material, adds to add various amylase behind the thermomaturation and carry out saccharification, produces glucose.

(2) fermentation of Aspergillus niger: saccharification liquid inoculated aspergillus niger, aspergillus niger becomes gluconic acid with glucose oxidase, by constantly pumping into CaCO ₃Acid in the slurry neutralise broth is proceeded fermentation, and the gluconic acid in the fermented liquid changes calglucon into.

(3) calglucon extracts: after the fermentation ends, and impurity such as filtering thalline, filtrate contains calglucon.Filtrate is concentrated into saturated under 100 ℃, at this moment contains calglucon 200g/L approximately.After being cooled to 20 ℃, leaving standstill 24h and allow crystallization separate out naturally or add crystal seed and promote crystallization to form.Use the small amount of ethanol washing crystal, then at 80 ℃ of drying under reduced pressure finished products.

China produces the factory of calglucon all with the form discharging of mother liquor after the calglucon crystallization with waste liquid, yet there are no the research that utilizes again about the gluconic acid mother liquor of calcium, and also not seeing has the people to prepare calglucon from mother liquor.

Through measuring, still contain the calglucon (measuring method and See Attachment 1) as a result of 5%-6% in the mother liquor, not only waste ample resources with discharging of waste liquid, simultaneously contaminate environment.If calglucon in the mother liquor further can be extracted, not only improved the utilization ratio of industrial raw material, economic benefit also increases.

Summary of the invention

The present invention is intended to calglucon in the mother liquor after the calglucon crystallization is further extracted, and a kind of method of extracting calglucon after the calglucon crystallization the mother liquor of high-efficient simple promptly is provided.

Concrete operating procedure method is as follows:

The method of extracting calglucon after the calglucon crystallization the mother liquor comprises removal of impurities, concentrated mother liquor, crystallization, process for separating and purifying step, and concrete steps are as follows:

A, removal of impurities

After the crystallization of 1000ml calglucon, add the 10g gac in the mother liquor, stir 8h, the filtered and recycled gac, mother liquor is standby after the removal of impurities;

B, concentrated

Get mother liquor 1000ml after the removal of impurities, under 100 ℃, be concentrated into and contain calglucon approximately, be cooled to 23-27 ℃ then, be concentrated into 590ml greater than 90g/L;

C, crystallization

Add edible ethanol in the concentrated cooled above-mentioned mother liquor of every 1000ml, making ultimate density is 12%, adds calglucon crystal seed 0.1g behind the mixing, leaves standstill 24h and allows crystallization separate out naturally;

D, separation are purified

The supernatant liquor that inclines, suction filtration with 50ml absolute ethanol washing crystal, becomes white granular calglucon finished product at 80 ℃ of drying under reduced pressure then; The purity of separating purification gained calglucon is greater than 95%.

Useful technique effect of the present invention is embodied in several aspects:

1, improves the utilization ratio of industrial raw material, increased the business economic benefit.Calculate to contain calglucon about 5.4% in the mother liquor, the gluconic acid calcium concn in the final waste liquid is less than 1.0% (about 0.9%); Every 1000kg gluconic acid mother liquor of calcium needs the 10kg gac, and the gac rate of recovery is 70%, 40 yuan of the expenses of gac, and 23 yuan of expenses such as the concentrated required energy, crystallization needs ethanol 80.4kg, and the rate of recovery 75%, ethanol expense are 61 yuan, 40 yuan of wage for workmen.26 yuan of other fees, can obtain calglucon (95% purity) 24.3kg market value is 10 yuan/kg, then every 1000kg mother liquor reclaims and can make a profit: 24.3 * 10-(40+23+61+40+26)=53 yuan, according to general enterprise industrial scale, year is handled 12000 tons, then year profit: ten thousand yuan of 53 * 12000=63.6.(Benefit Calculation and the results are shown in annex five).

2, removed the impurity in the mother liquor after the calglucon crystallization in preparation engineering, and calglucon is reclaimed, the ethanol behind the secondary crystal reclaims by distillation, and the waste liquid organic content of eliminating reduces greatly, has reduced environmental pollution, has increased social benefit.

3, the present invention has filled up the technological gap that extracts calglucon after the calglucon crystallization the mother liquor.

Embodiment

Embodiment:

The first step:

The calglucon that not only contains a great deal of in the mother liquor after the calglucon crystallization also contains impurity such as collagen protein, pigment, polysaccharide simultaneously, and these impurity hinder the crystallization of calglucon, handles so at first will carry out removal of impurities.Get the mother liquor (containing calglucon 5.4% approximately) after 1000L (being 1000kg) the calglucon crystallization, add the gac of 10kg, do not stop under the stirring condition impurity to be carried out adsorption-edulcoration at stirrer, adsorption time is 8 hours, then the filtered and recycled gac.

Activated carbon dosage is as follows to adsorption effect influence test:

(1) method

Get 13 250ml Erlenmeyer flasks, each Erlenmeyer flask pipe adds 100 milliliters of original nut liquids, adds gac respectively: 0.00 gram, 0.20 gram, 0.40 gram, 0.60 gram, 0.80 gram, 1.00 grams, 1.20 grams, 1.40 grams, 1.60 grams, 1.80 grams, 2.00 grams, 2.20 grams, 2.40 grams.Shook 8 hours, centrifugal, observe the decolouring situation, and measure the BSA value of 280nm.

(2) result

Protein the results are shown in following table in the different activities charcoal absorption mother liquor.

The pipe number	1	2	3	4	5	6	7	8	9	10	11	12	13
														Gac (g)	0.00	0.20	0.40	0.60	0.80	1.00	1.20	1.40	1.60	1.80	2.00	2.20	2.40
BSA	7.83	6.34	5.67	4.10	2.40	1.23	1.11	0.98	0.89	0.86	0.82	0.84	0.81

As can be seen from the above table, activated carbon dosage is big more, and is big more within the specific limits to absorption of proteins, and it is also complete more to decolour, and considers the industrial production cost, has selected for use 10.g gac/L proper.

Second step:

Mother liquor after the charcoal absorption is heated to 100 ℃, and distillation is concentrated into mother liquor and contains calglucon 9% (being 90g/L) under this temperature, and cycles of concentration is about 1.67 times, is cooled to 23-27 ℃ then.

The 3rd step:

The ethanol (100% concentration) of getting 80.4kg is to cooled mother liquor central (590L), and mixing adds calglucon crystal seed 100g, leaves standstill 24h and allows the calglucon crystallization separate out naturally.The supernatant liquor that inclines, suction filtration with 10L absolute ethanol washing crystal, is dried to finished product then under 80 ℃ of reduced pressure.Final calglucon (the about 95% purity) 24.3kg that obtains.

The most definite test of suitable alcohol concn is as follows:

1 method

Get 13 100ml beakers, each beaker adds mother liquor concentrated solution (containing calglucon 20%) 9 milliliters, adds the second alcohol and waters of the different amounts of ethanol respectively, and making cumulative volume is 20ml, and concentration of ethanol is at 8-20%.It is brilliant female to add a small amount of calglucon, and crystallization is 24 hours under the room temperature, and is centrifugal, with absolute ethanol washing once, and 80 ℃ of dryings, weighing, record.

2 results

Different ethanol concentration sees the following form to the test-results of mother liquor concentrated solution crystallization effect.

The pipe number	1	2	3	4	5	6	7	8	9	10	11	12	13
														20% glucose (ml)	9	9	9	9	9	9	9	9	9	9	9	9	9
Water (ml)	8.4	8.2	8.0	7.8	7.6	7.4	7.2	7.0	6.8	6.6	6.4	6.2	6.0
														Dehydrated alcohol (ml)	1.6	1.8	2.0	2.2	2.4	2.6	2.8	3.0	3.2	3.4	3.6	3.8	4.0
Cumulative volume (ml)	20	20	20	20	20	20	20	20	20	20	20	20	20
														Glucose concn (%)	9	9	9	9	9	9	9	9	9	9	9	9	9
Alcohol concn (%)	8	9	10	11	12	13	14	15	16	17	18	19	20
														Crystalline calglucon heavy (g)	0.90	1.11	1.32	1.45	1.6	1.63	1.63	1.67	1.69	1.70	1.73	1.72	1.73

As can be seen from the above table, concentration of ethanol is big more, and the calglucon crystallization is complete more, considers the industrial production cost, has selected for use alcohol concn 12% proper.

Claims (1)

1, extract the method for calglucon after the calglucon crystallization the mother liquor, it is characterized in that: comprise removal of impurities, concentrated mother liquor, crystallization, process for separating and purifying step, concrete operation method is as follows:

A, removal of impurities

After the crystallization of 1000ml calglucon, add the 10g gac in the mother liquor, stir 8h, the filtered and recycled gac, mother liquor is standby after the removal of impurities;

B, concentrated

Get mother liquor 1000ml after the removal of impurities, under 100 ℃, be concentrated into and contain calglucon approximately, be cooled to 23-27 ℃ then, be concentrated into 590ml greater than 90g/L;

C, crystallization

Add edible ethanol in the concentrated cooled above-mentioned mother liquor of every 1000ml, making ultimate density is 12%, adds calglucon crystal seed 0.1g behind the mixing, leaves standstill 24h and allows crystallization separate out naturally;

D, separation are purified

The supernatant liquor that inclines, suction filtration with 50ml absolute ethanol washing crystal, becomes white granular calglucon finished product at 80 ℃ of drying under reduced pressure then; The purity of separating purification gained calglucon is greater than 95%.