CN106146290A - A kind of method producing calcium citrate salts - Google Patents
A kind of method producing calcium citrate salts Download PDFInfo
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- CN106146290A CN106146290A CN201510155996.8A CN201510155996A CN106146290A CN 106146290 A CN106146290 A CN 106146290A CN 201510155996 A CN201510155996 A CN 201510155996A CN 106146290 A CN106146290 A CN 106146290A
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- citric acid
- calcium
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- aqueous
- calcium citrate
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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
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Abstract
The invention discloses a kind of method producing calcium citrate salts, wherein, the method includes: the reactant mixture obtained, at 0-30 DEG C, by least one the calcium source in ground calcium carbonate, calcium hydroxide and calcium oxide and aqueous citric acid solution haptoreaction, and is filtered by (1)；(2) filtrate after filtering in step (1) is heated so that calcium citrate salts Precipitation, be then demultiplex out calcium citrate salts and precipitate and wash.American Pharmacopeia USP 33-NF 28 and the high-purity citric acid calcium salt of U.S. food additive FCC5 standard can be met with low-cost production by the method.
Description
Technical field
The invention belongs to field of fine chemical, in particular it relates to a kind of method producing calcium citrate salts.
Background technology
Calcium citrate salts is a kind of excellent nutrition enhancer, chelating agent, solution buffer agent, food,
The field such as medical and chemical has important using value.
At present, the method obtaining calcium citrate salts can not take into account high-purity and low cost simultaneously.Such as, make
React with high-purity citric acid (aqueous solution) by purity calcium carbonate (or calcium hydroxide, calcium oxide) and obtain
Obtain calcium citrate solid, although the method can obtain highly purified calcium citrate salts, but in the method
Required purity calcium carbonate needs to use ground calcium carbonate, hydrochloric acid to refine with sodium carbonate, and citric acid to use
Food stage citric acid, therefore cost is the highest；It addition, prior art often uses Fructus Citri Limoniae at relatively high temperatures
The method that acid and calcium carbonate (or calcium hydroxide, calcium oxide) generate calcium citrate salts solid as raw material,
But the impurity that the raw material of the method and intermediate steps introduce is difficult to remove, and the purity of calcium citrate product is difficult to
Ensure.
Therefore, this area needs a kind of cost of exploitation relatively low and is obtained in that to meet country and company standard reaches
To American Pharmacopeia USP 33-NF 28 and the high-purity citric acid calcium salt of U.S. food additive FCC5 standard
Production method.
Summary of the invention
It is an object of the invention to overcome in existing production calcium citrate salts method and can not take into account height simultaneously
Purity and the defect of low cost, it is provided that a kind of method producing high-purity citric acid calcium salt of low cost.
To achieve these goals, the present invention provides a kind of method producing calcium citrate salts, wherein, is somebody's turn to do
Method includes:
(1) at 0-30 DEG C, by least one calcium in ground calcium carbonate, calcium hydroxide and calcium oxide
Source and aqueous citric acid solution haptoreaction, and the reactant mixture obtained is filtered；
(2) filtrate after filtering in step (1) is heated so that calcium citrate salts Precipitation,
It is then demultiplex out calcium citrate salts precipitation.
The calcium citrate product salt using the inventive method to obtain can reach American Pharmacopeia USP after testing
33-NF 28 and the standard of U.S. food additive FCC5.It addition, the method provided according to the present invention,
Without using highly purified raw material, greatly reduce production cost.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the flow process of a kind of detailed description of the invention of the method producing calcium citrate salts according to the present invention
Schematic diagram.
Fig. 2 is the stream of the another kind of detailed description of the invention of the method producing calcium citrate salts according to the present invention
Journey schematic diagram.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method producing calcium citrate salts, wherein, the method includes:
(1) at 0-30 DEG C, by least one calcium in ground calcium carbonate, calcium hydroxide and calcium oxide
Source and aqueous citric acid solution haptoreaction, and the reactant mixture obtained is filtered；
(2) filtrate after filtering in step (1) is heated so that calcium citrate salts Precipitation,
It is then demultiplex out calcium citrate salts precipitation.
According to the present invention, wherein, in step (1), the citric acid in described aqueous citric acid solution with
The mol ratio of the calcium constituent in described calcium source can be more than 2.1:1；Under preferable case, described citric acid
Citric acid in aqueous solution is 2.1-20:1 with the mol ratio of the calcium constituent in described calcium source.
According to the present invention, in step (1), described catalytic process does not has special restriction,
The most described catalytic process may include that to join in aqueous citric acid solution described calcium source and carries out
Haptoreaction.
According to the present invention, in order to make calcium source and aqueous citric acid solution carry out being fully contacted reaction, described
Calcium source or is joined in aqueous citric acid solution by certain speed the most in batches.It is further preferred that it is described
Calcium source adds the mode of aqueous citric acid solution: relative to aqueous citric acid solution described in 1L, by described calcium
Source joins with the speed of 0.1-1g/s and carries out haptoreaction in aqueous citric acid solution.
Wherein, described calcium source can join in aqueous citric acid solution with the form of its serosity.Calcium source serosity
There is no particular limitation with the water content in aqueous citric acid solution, under preferable case, and calcium source serosity and Fructus Citri Limoniae
Water in the mixture that water content in aqueous acid is obtained after making reaction and the mol ratio of calcium constituent
For more than 25:1, more preferably 25-100:1.
According to the present invention, in step (1), the mixture obtained after haptoreaction is filtered,
Thus filter out the insoluble matter in solution.The filter method that described filtration can use this area conventional enters
OK, such as plate-and-frame filtration or micro-filtrate membrane filtration method, when using plate-and-frame filtration method, can be in advance at plate
In frame, precoated diatomite or perlite form filter aid filter cake, make solution pass through sheet frame the most again, carry out
Filter.
According to the present invention, the kind of described aqueous citric acid solution is not particularly limited, such as described
Aqueous citric acid solution can be the aqueous citric acid solution prepared of citric acid extraction technique, oil product be raw material
Aqueous citric acid solution, citric acid fermentation aqueous solution, Mother Liquor of Crystallizing Citric Acid and the ion-exchange treatment of preparation
At least one in aqueous citric acid solution, under preferable case, described aqueous citric acid solution is citric acid fermentation
At least one in the aqueous citric acid solution of clear liquid, Mother Liquor of Crystallizing Citric Acid and ion-exchange treatment.
Described citric acid fermentation aqueous solution can be by the citric acid fermentation broth liquid through being filtrated to get, Yi Yishui
Citrometer, in described citric acid fermentation aqueous solution, the content of citric acid can be 40-200g/L.Described lemon
Lemon acid crystal mother solution can be the mother solution after Citric Acid Production crystallization, in terms of citric acid monohydrate, described Fructus Citri Limoniae
In acid crystal mother solution, the content of citric acid can be 600-800g/L.The citric acid of described ion-exchange treatment
Aqueous solution can be the solution that individually processes through cation exchange resin of Citric Acid Production or through cation and
The solution of anion exchange resin process, in terms of citric acid monohydrate, the citric acid of described ion-exchange treatment
In aqueous solution, the content of citric acid can be more than 200gL and less than 600g/L.
The preparation method of described aqueous citric acid solution can use commonly used in the art prepares citric acid
The method of aqueous solution.To the turbidity of prepared aqueous citric acid solution, there is no particular limitation, such as citric acid
The turbidity of aqueous solution can be less than or equal to 20NUT.
According to the present invention, utilize the deliquescent feature of calcium citrate salts, calcium citrate can be made by heating
Salt filter from step (1) after solution in separate out, it is contemplated that productivity and production efficiency, when described lemon
When lemon acid calcium salt is calcium citrate, under preferable case, in described aqueous citric acid solution, the content of citric acid is
40-120g/L；Step (2) described filtrate is heated to 65-90 DEG C, and the programming rate of heating is 5-10 DEG C/min；
Citric acid in described aqueous citric acid solution is 2.1-3.0:1 with the mol ratio of the calcium constituent in described calcium source.
According to the present invention, when described calcium citrate salts is calcium hydrogen citrate, the Fructus Citri Limoniae that heated solution separates out
Acid hydrogen calcium can be contaminated with a small amount of calcium citrate.The present inventor finds through in-depth study, will
Described filtrate is heated to 65-90 DEG C, and keeps more than 30min i.e. to can get pure lemon at such a temperature
Lemon acid hydrogen calcium.In view of production efficiency, when described calcium citrate salts is calcium citrate, under preferable case,
In described aqueous citric acid solution, the content of citric acid is more than 120g/L and less than or equal to 800g/L；Step (2)
Described filtrate is heated to 65-90 DEG C, and keeps 30-60min at such a temperature, and the programming rate of heating is
Less than 5 DEG C/min；Calcium constituent in citric acid in described aqueous citric acid solution and described calcium source mole
Than more than 3.0:1 and less than or equal to 20:1.
The mode of described heating can be that mode of heating commonly used in the art is carried out, such as, can be water
Bath heating, oil bath heating, electrical heating and steam heating.
In the present invention, for improving the quality of the final calcium citrate salts obtained precipitation further, preferably exist
Before solution processes after heating and filtering and/or in, in solution, put into a small amount of calcium citrate salts crystal seed.
In the present invention, for improving the production efficiency of calcium citrate salts further, at heating or the bar of insulation
Can also be stirred under part.Described stirring can be the method that this area is conventional, does not repeats them here.
In the present invention, the method for separation of citric acid calcium precipitation is not particularly limited, such as
Calcium citrate salts precipitation is separated by the method that can use sucking filtration.The present invention lemon to being isolated to
The content of the free water in lemon acid calcium salt is not particularly limited, the calcium citrate of the most separated acquisition
In salt precipitation, the content of free water is 10-50 weight %, more preferably 15-30 weight %.
According to the present invention, when the calcium citrate salts precipitation color of isolated is deeper, under preferable case,
The method is additionally included in before heating filtrate, described filtrate is decoloured, the side of described decolouring
Method can be described filtrate to be contacted with decolorising agent, and described decolorising agent can be commonly used in the art taking off
Toner, the most described decolorising agent can be activated carbon.In order to ensure decolorizing effect, under preferable case, institute
State decolouring to carry out at 0-30 DEG C.
In the present invention, for the not spy of ground calcium carbonate, calcium hydroxide and the calcium oxide as calcium source
Other restriction, can select the product that this area is conventional.In one embodiment, the method for the present invention
The calcium source that impurity content can be used to be below 10 weight %, preferably impurity content are the calcium of 1-5 weight %
Source.Described impurity refers to the impurity generally comprised in calcium product-derived, such as silicon dioxide, heavy metal compound
With one or more in insoluble silicate.Described heavy metal compound can be such as copper, lead, zinc,
At least one in the compound of stannum, nickel, cobalt, antimony, hydrargyrum, cadmium and bismuth.Described insoluble silicate example
As being Anhydrite K2Al2Si6O16Or asbestos CaMg3Si4O12。
Described ground calcium carbonate can be natural whiting.The granularity of described ground calcium carbonate is the most especially
Restriction, can be such as 10-400 micron, preferably 80-200 micron.In the present invention, described
Granularity refers to the maximum linear distance between two differences on granule, when granule is spherical, then should
The granularity of granule refers to the diameter of this granule.
In the method producing calcium citrate salts that the present invention provides, under preferable case, it is right that the method also includes
The calcium citrate salts precipitation of isolated carries out except lead successively, washs and dry, to improve product further
Purity and quality.
Wherein, except the method for lead is method commonly used in the art, for example, it is possible to be in isolated
Calcium citrate salt system in add spirit of vinegar reactant is eluriated, concrete operation method can be:
The calcium citrate salts of isolated is transferred in reaction pot, relative to 100kg calcium citrate salts, adds
The concentration of 20-40mL is the dilute acetic acid solution of 20 weight %, and is stirred 15-20 minute.
Wherein, the method for washing can use the various methods that this area is conventional, the bar of the most described washing
Part includes using deionized water, and water temperature is 75-85 DEG C, is washed till calcium citrate salts precipitation without acetic acid smell.
Wherein, the method for drying can use the various methods that this area is conventional, the bar of the most described drying
Part includes that the temperature dried is 80-85 DEG C, and the time of drying is 0.5-1h.
Fig. 1 is the schematic flow sheet producing calcium citrate according to the method for the present invention.Specifically, by calcium source
Join and aqueous citric acid solution carries out haptoreaction, then the reactant mixture obtained was filtered
Miscellaneous, then filtrate and activated carbon are carried out contact decolorization, then the filtrate after activated carbon decolorizing is carried out
Heat and stir precipitation precipitation, then using acetic acid and water to wash, finally successively obtained precipitation
Dry.
Fig. 2 is the schematic flow sheet producing calcium hydrogen citrate according to the method for the present invention.Specifically, by calcium
Source joins and carries out haptoreaction in aqueous citric acid solution, is then filtered by the reactant mixture obtained
Remove impurity, then carries out contact decolorization by filtrate and activated carbon, then the filtrate after activated carbon decolorizing is entered
Row is slowly heated and stirs precipitation precipitation, and is heated to during temperature of the present invention being incubated and stirring
Mix, use acetic acid and water to wash the most successively obtained precipitation, finally dry.
Hereinafter by specific embodiment, the present invention will be further described in detail.
In following preparation example, embodiment and comparative example:
1, in aqueous citric acid solution, the content of citric acid is titrated by 0.1429mol/L sodium hydrate aqueous solution
Method be measured.
2, the turbidity of aqueous citric acid solution is turbid by the WZS-200 type of upper dried shrimps Qing Ke necessary instrument company
Degree meter is measured.
3, calcium citrate salts washing of precipitate water potassium permanganate oxidation accounts for the color time and records by the following method: use
Deionized water wash 1g (in terms of butt) the calcium citrate salts moist precipitate of 100mL, 75-95 DEG C, then
Carrying out filtering to isolate calcium citrate salts, the filtered solution obtained after being filtered by 25mL is placed in color comparison tube,
Then the color comparison tube filling filtrate is positioned over 3min in the water-bath of 25 DEG C, then drips in color comparison tube
Enter the potassium permanganate solution of 21 weight ‰, observe and record potassium permanganate oxidation account for color (ie in solution in
Existing blush) time.
Wherein, owing to becoming colourless or other colors after potassium permanganate solution oxidation of organic compounds (reduzate),
These can be mainly saccharide by oxidized Organic substances, and therefore, described potassium permanganate oxidation accounts for the color time and refers to
Potassium permanganate solution instills the time (invariant color time) keeping primary colors in calcium citrate salts washing of precipitate water；
The time keeping primary colors is the longest, illustrates that the effect of the impurity such as eluting saccharide is the best.
4, lead content in the purity of calcium citrate product salt and calcium citrate product salt is according to GB
In 1987-2007, the method for regulation is measured and calculates.
5, the easy charcoal multiple of calcium citrate salts according to: in GB 17203-1998 regulation method be measured
And calculating.
6, the assay method of hydrochloric acid insoluble substance is as follows: the 5g that materialses (is accurate to 0.001g), adds 6mol
Hydrochloric acid 10ml and water 50ml, mixes post-heating 30min, with No. three sand core funnel vacuum filtrations, uses 200ml
Water flushes three times, and precipitate is dried 2h at 105 DEG C.The hydrochloric acid insoluble substance of national regulations i.e. residue should
Less than 10mg (i.e. 0.2%).
7, content of beary metal according to: in GB/T 5009.74-2003 regulation method be measured and calculate.
8, arsenic content according to: in GB/T 7686-2008 regulation method be measured and calculate.
9, content of fluoride according to: in GB 7484-87 regulation method be measured and calculate.
Preparation example 1
This preparation example is for illustrating the preparation of citric acid fermentation aqueous solution.
0.872 kg corn SFSP series beater disintegrating machine is pulverized, obtains average grain
A diameter of 2 millimeters (the Accu Sizer TM 780 optics droplet measurement instrument using PPS company of the U.S. is surveyed
0.871 kilogram of crushed products calmly)；Crushed products is mixed with amylase and carries out injection liquefaction, once
It is 83 ± 1 DEG C that liquefaction controls temperature, and once liquefaction is held time as 2-5 minute, and secondary liquefaction controls temperature
Degree is 93 ± 1 DEG C, and secondary liquefaction was held time as 90-150 minute, and (pH value of described enzymolysis maintains
5.7-6.2；In terms of the dry weight of every gram of crushed products, the consumption of α-amylase (purchased from Novozymes Company) is
40 enzyme activity units, wherein, the definition of enzyme activity unit is: pH value be 6.0, temperature be 70 DEG C
Under conditions of, 1 minute by 1 milligram of Starch Conversion be the enzyme amount needed for reducing sugar be an enzyme activity list
Position), obtain enzymatic hydrolysate.
By Partial digestion product by carrying out filter pressing with fluid pressure type filter press, isolate clear liquid and filter
Slag, wherein, the solid content of filtering residue is 50 weight %.
The fermentation tank of 300L will be joined after the clear liquids of 172.8 kilograms, 43.2 kilograms of enzymatic hydrolysate sterilizings
In, obtain fermentation medium.
Partial digestion product obtained above is diluted with water to total sugar is 10 weight %, obtains seed training
Support base, seed culture medium is put into seed tank, is heated to 121 DEG C of sterilizations, fast prompt drop after maintaining 30 minutes
Temperature, to 36 DEG C, accesses aspergillus niger strain, and in every liter of seed culture medium, the inoculum concentration of aspergillus niger is 2 × 108
Individual spore.36 DEG C, initial ph value be 5.5,0.6 volume: the aeration condition of (volume minute)
Under carry out spawn culture；The life to aspergillus niger is measured by sampling sediments microscope inspection, acidity assaying and pH
Long observing, as pH ＜ 2.0, acidity ＞ 1g/100mL, fungus ball size is uniform, mycelia is sturdy stretches out
Time, stop cultivating.
Aspergillus niger strain through cultivating is joined and fermentation tank starts fermentation, in every liter of fermentation medium
Inoculum concentration is 2.2 × 107 spores, and fermentation condition includes that temperature is 36 DEG C, and initial ph value is 4.5, logical
Tolerance is 0.8 volume: (volume minute), and fermentation to content of reducing sugar in fermentation liquid reaches 0.3g/100mL
Hereinafter stop fermentation, then carry out being filtrated to get citric acid fermentation aqueous solution by the fermentation liquid obtained.
After measured, in citric acid fermentation aqueous solution, the content of citric acid is 105g/L, citric acid fermentation aqueous solution
Turbidity is 9NTU.
Preparation example 2
This preparation example is for illustrating the preparation of Mother Liquor of Crystallizing Citric Acid.
At a temperature of 75 DEG C, the citric acid magma machine by centrifugation containing anhydrous citric acid crystal is separated
Obtain aqueous citric acid solution after anhydrous citric acid, then the aqueous citric acid solution obtained is cooled to 30 DEG C, so
Rear filtration is lowered the temperature, and separates out Citric acid crystal and obtains Mother Liquor of Crystallizing Citric Acid.
After measured, in Mother Liquor of Crystallizing Citric Acid, the content of citric acid is 800g/L, Mother Liquor of Crystallizing Citric Acid
Turbidity is 8NTU.
Embodiment 1
The present embodiment is for illustrating the method producing calcium citrate salts that the present invention provides.
(1) at 20 DEG C, by 100g ground calcium carbonate, (purity 97%, granularity 350 μm are purchased from mountain
Dong Ke source pharmaceutical Co. Ltd) citric acid of 4L preparation example 1 gained is joined with the addition speed of 1g/s
Fermentation clear liquid carries out haptoreaction, the reactant mixture obtained is filtered, then will at 20 DEG C
Filtrate and activated carbon carry out contact decolorization.
(2) filtrate of gained adds after step (1) is decoloured 0.2g calcium citrate crystal seed, and with 5 DEG C
The programming rate of/min is heated to 80 DEG C to filtrate, obtains white calcium citrate precipitation, and sucking filtration obtains wet lemon
Lemon acid calcium deposit (free water content is 30 weight %).
(3) calcium citrate of isolated is transferred in reaction pot, relative to 100kg calcium citrate
Salt, adds the dilute acetic acid solution that concentration is 20 weight % of 20mL, stirs 20 minutes, acetic acid of draining
Solution.It is then used by the deionized water of 80 DEG C, calcium citrate precipitation is washed till without acetic acid smell so that Fructus Citri Limoniae
Acid calcium deposit washings potassium permanganate oxidation accounts for the color time more than or equal to 10min, and to obtain moisture be 40
Weight %, the easy charcoal multiple calcium citrate less than or equal to 1.
(4) calcium citrate of above-mentioned steps (3) gained is dried 0.9h at 80 DEG C, then measure lemon
The purity of lemon acid calcium, hydrochloric acid insoluble substance content, content of beary metal, lead content, arsenic content and fluoride contain
Amount, result is as shown in table 1.
Embodiment 2
The present embodiment is for illustrating the method producing calcium citrate salts that the present invention provides.
(1) at 20 DEG C, by 100g ground calcium carbonate, (purity 95.5%, granularity 150 μm are purchased from river
The rich Pharmaceuticals Ltd of Su Yuan) join 600mL preparation example 1 gained with the addition speed of 0.1g/s
Mother Liquor of Crystallizing Citric Acid carries out haptoreaction, the reactant mixture obtained is filtered, then exists
At 15 DEG C, filtrate and activated carbon are carried out contact decolorization.
(2) filtrate of gained adds after step (1) is decoloured 0.15g calcium citrate crystal seed, and with
The programming rate of 10 DEG C/min is heated to 65 DEG C to filtrate, obtains white calcium citrate precipitation, and sucking filtration obtains
Wet calcium citrate precipitation (content of free water is 10 weight %).
(3) calcium citrate of isolated is transferred in reaction pot, relative to 100kg calcium citrate
Salt, adds the dilute acetic acid solution that concentration is 20 weight % of 20-40ml, stirs 20 minutes, vinegar of draining
Acid solution.It is then used by the deionized water of 80 DEG C, calcium citrate precipitation is washed till without acetic acid smell so that lemon
Lemon acid calcium washings potassium permanganate oxidation accounts for the color time more than or equal to 10min, and to obtain moisture be 40 weights
Amount %, the easy charcoal multiple calcium citrate less than or equal to 1.
(4) calcium citrate of above-mentioned steps (3) gained is dried 0.8h at 83 DEG C, then measure lemon
The purity of lemon acid calcium, hydrochloric acid insoluble substance content, content of beary metal, lead content, arsenic content and fluoride contain
Amount, result is as shown in table 1.
Embodiment 3
The present embodiment is for illustrating the method producing calcium citrate salts that the present invention provides.
(1) at 20 DEG C, by 100g ground calcium carbonate, (purity 96.5%, granularity 260 μm are purchased from
SeaBird space Chemical Co., Ltd.) citric acid of 6L preparation example 2 gained is joined with the addition speed of 2g/s
Fermentation clear liquid is reacted, the reactant mixture obtained is filtered, then by filtrate at 20 DEG C
Contact decolorization is carried out with activated carbon.
(2) filtrate of gained adds after step (1) is decoloured 0.18g calcium hydrogen citrate crystal seed, and
With the programming rate of 3 DEG C/min, filtrate is heated to 85 DEG C and insulated and stirred 1h, obtains white citric acid
Hydrogen calcium deposit, sucking filtration obtains wet hydrogen citrate calcium deposit (free water content is 40 weight %).
(3) calcium hydrogen citrate of isolated is transferred in reaction pot, relative to 100kg citric acid
Calcium salt, adds the dilute acetic acid solution that concentration is 20 weight % of 40mL, stirs 15 minutes, vinegar of draining
Acid solution.It is then used by the deionized water of 85 DEG C, calcium citrate precipitation is washed till without acetic acid smell so that lemon
Lemon acid hydrogen calcium washings potassium permanganate oxidation accounts for the color time more than or equal to 10min, and to obtain moisture be 45
Weight %, the easy carbon multiple calcium hydrogen citrate less than or equal to 1.
(4) calcium hydrogen citrate of above-mentioned steps (3) gained is dried 0.7h at 80 DEG C, then measure
The purity of calcium hydrogen citrate, hydrochloric acid insoluble substance content, content of beary metal, lead content, arsenic content and fluorination
Thing content, result is as shown in table 1.
Embodiment 4
The present embodiment is for illustrating the method producing calcium citrate salts that the present invention provides.
(1) at 20 DEG C, by 100g ground calcium carbonate, (purity 93%, granularity 600 μm are purchased from
SeaBird space Chemical Co., Ltd.) join 1200mL preparation example 2 gained with the addition speed of 0.5g/s
Mother Liquor of Crystallizing Citric Acid carries out haptoreaction, the reactant mixture obtained is filtered, then exists
At 20 DEG C, filtrate and activated carbon are carried out contact decolorization.
(2) filtrate of gained adds after step (1) is decoloured 0.5g calcium hydrogen citrate crystal seed, and with
The programming rate of 4 DEG C/min is heated to 90 DEG C and insulated and stirred stirring 50min to filtrate, obtains white lemon
Lemon acid hydrogen calcium deposit, sucking filtration obtains wet hydrogen citrate calcium deposit (free water content is 50 weight %).
(3) calcium citrate of isolated is transferred in reaction pot, relative to 100kg calcium citrate
Salt, adds the dilute acetic acid solution that concentration is 20 weight % of 30mL, stirs 15 minutes, acetic acid of draining
Solution.It is then used by the deionized water of 80 DEG C, calcium citrate precipitation is washed till without acetic acid smell so that Fructus Citri Limoniae
Acid hydrogen calcium washings potassium permanganate oxidation accounts for the color time more than or equal to 10min, and to obtain moisture be 40 weights
Amount %, the easy charcoal multiple calcium hydrogen citrate less than or equal to 1.
(4) calcium hydrogen citrate of above-mentioned steps (3) gained is dried 0.5h at 83 DEG C, then measure
The purity of calcium hydrogen citrate, hydrochloric acid insoluble substance content, content of beary metal, lead content, arsenic content and fluorination
Thing content, result is as shown in table 1.
Comparative example 1
(1) (content of citric acid is aqueous citric acid solution food stage citric acid and pure water being configured to
400g/L, turbidity is 0.8NTU).By following mol ratio: ground calcium carbonate: 15 weight % hydrochloric acid (with
Hydrogen chloride meter)=1:2.5 makes calcium chloride solution, carries out, after fully reaction, the acquisition chlorine that filters and decolour
Change calcium solution.By prepared calcium chloride solution (calcium chloride content accounts for 40 weight %) by following mole
Ratio reacts with sodium carbonate, calcium chloride: sodium carbonate=1:2, prepares calcium carbonate.
(2) by calcium carbonate successively through being dehydrated, washing, be dried and cooling after with aqueous citric acid solution (institute
Stating citric acid is to meet the edible citric acid that GB 2760-2011 specifies) and water according to following mol ratio,
Calcium carbonate: the amount of the citric acid in aqueous citric acid solution: water=1:0.67:44 is configured to solution at 80 DEG C
Under conditions of react, after reaction terminates, relative to 100kg calcium citrate salts, add 30mL's
Concentration is the dilute acetic acid solution of 20 weight %, is stirred 15 minutes, then uses the deionization of 80 DEG C
Water washing calcium citrate crystals is precipitated to without acetic acid smell so that calcium hydrogen citrate washings potassium permanganate oxidation
Account for the color time more than or equal to 10min, and to obtain moisture be that 30 weight %, easy charcoal multiple are less than or equal to 1
Calcium hydrogen citrate.
(3) calcium citrate of above-mentioned gained is dried 1h at 83 DEG C, then measure the pure of calcium citrate
Degree, hydrochloric acid insoluble substance content, content of beary metal, lead content, arsenic content and content of fluoride, result is such as
Shown in table 1.
Table 1
From the result of embodiment 1-4 and comparative example 1 it can be seen that use the production Fructus Citri Limoniae that the present invention provides
The method of acid calcium salt, it is not necessary to use high-purity citric acid, calcium carbonate, calcium hydroxide and calcium oxide etc. to make former
Material, can obtain and highly purified meet American Pharmacopeia USP 33-NF 28 and U.S. food additive FCC5
The calcium citrate salts of standard, eliminates the process such as refined of the raw materials such as calcium carbonate, is reaching and prior art
While same effect, significantly reduce the cost producing calcium citrate salts, there is huge using value.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
Claims (10)
1. the method producing calcium citrate salts, it is characterised in that the method includes:
(1) at 0-30 DEG C, by least one calcium in ground calcium carbonate, calcium hydroxide and calcium oxide
Source and aqueous citric acid solution haptoreaction, and the reactant mixture obtained is filtered；
(2) filtrate after filtering in step (1) is heated so that calcium citrate salts Precipitation,
It is then demultiplex out calcium citrate salts precipitation.
Method the most according to claim 1, wherein, in step (1), described citric acid water
Citric acid in solution is 2.1-20:1 with the mol ratio of the calcium constituent in described calcium source.
Method the most according to claim 1, wherein, in step (1), described haptoreaction
Process include: described calcium source is joined aqueous citric acid solution carries out haptoreaction.
Method the most according to claim 3, wherein, relative to aqueous citric acid solution described in 1L,
Described calcium source is joined with the speed of 0.1-1g/s aqueous citric acid solution carries out haptoreaction.
5. according to the method described in any one in claim 1-4, wherein, described citric acid is water-soluble
Liquid is in the aqueous citric acid solution of citric acid fermentation aqueous solution, Mother Liquor of Crystallizing Citric Acid and ion-exchange treatment
At least one；
Described citric acid fermentation aqueous solution is by the citric acid fermentation broth liquid through being filtrated to get, with a water Fructus Citri Limoniae
Acid meter, in described citric acid fermentation aqueous solution, the content of citric acid is 40-200g/L；
Described Mother Liquor of Crystallizing Citric Acid is the mother solution after Citric Acid Production crystallization, in terms of citric acid monohydrate, institute
Stating the content of citric acid in Mother Liquor of Crystallizing Citric Acid is 600-800g/L；
The aqueous citric acid solution of described ion-exchange treatment is that Citric Acid Production is individually through cation exchange tree
Fat process solution or through cation and the solution of anion exchange resin process, with citric acid monohydrate
Meter, in the aqueous citric acid solution of described ion-exchange treatment, the content of citric acid is more than 200gL and to be less than
600g/L。
Method the most according to claim 1, wherein, described calcium citrate salts is calcium citrate,
In described aqueous citric acid solution, the content of citric acid is 40-120g/L；Step (2) described filtrate is heated to
65-90 DEG C, the programming rate of heating is 5-10 DEG C/min；Citric acid in described aqueous citric acid solution and institute
The mol ratio stating the calcium constituent in calcium source is 2.1-3.0:1.
Method the most according to claim 1, wherein, described calcium citrate salts is calcium hydrogen citrate,
In described aqueous citric acid solution, the content of citric acid is more than 120g/L and less than or equal to 800g/L；Step (2)
Described filtrate is heated to 65-90 DEG C, and keeps 30-60min at such a temperature, and the programming rate of heating is
Less than 5 DEG C/min；Calcium constituent in citric acid in described aqueous citric acid solution and described calcium source mole
Than more than 3.0:1 and less than or equal to 20:1.
Method the most according to claim 1, wherein, the method is additionally included in be entered described filtrate
Before row heating, described filtrate being decoloured, the method for described decolouring is by described filtrate and decolorising agent
Contact, the temperature of contact is 0-30 DEG C, and described decolorising agent is activated carbon.
Method the most according to claim 1, wherein, after the method is additionally included in step (2),
The calcium citrate salts precipitation of isolated is carried out except lead successively, washs and dry.
Method the most according to claim 1, wherein, the miscellaneous of 1-5 weight % is contained in described calcium source
Matter, and described impurity is one or more in silicon dioxide, heavy metal compound and insoluble silicate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108218694A (en) * | 2018-01-30 | 2018-06-29 | 日照金禾博源生化有限公司 | A kind of preparation method of ultra-fine calcium citrate |
| CN112047833A (en) * | 2019-06-05 | 2020-12-08 | 上海固钛实业有限公司 | Preparation method of citric acid |
| CN112409167A (en) * | 2020-11-27 | 2021-02-26 | 日照金禾博源生化有限公司 | Preparation method of calcium citrate whisker |
| CN114573442A (en) * | 2020-11-30 | 2022-06-03 | 南通星辰合成材料有限公司 | Treatment method of reaction waste liquid in polyphenyl ether synthesis process |
| CN115212815A (en) * | 2022-08-13 | 2022-10-21 | 山东巨展新材料有限公司 | Preparation method of water-soluble citric acid colloid |
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| CN1719986A (en) * | 2002-11-22 | 2006-01-11 | 萨拉·A.·卡拉比尼 | Calcium fortified acidic beverages |
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| CN102476993A (en) * | 2010-11-26 | 2012-05-30 | 中粮生物化学（安徽）股份有限公司 | Preparation method of sodium citrate |
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| CN1066443A (en) * | 1992-06-25 | 1992-11-25 | 上海川沙恒大商行 | Produce the method for high purity medical citrate of lime with ordinary student lime and edible citric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108218694A (en) * | 2018-01-30 | 2018-06-29 | 日照金禾博源生化有限公司 | A kind of preparation method of ultra-fine calcium citrate |
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| CN112047833A (en) * | 2019-06-05 | 2020-12-08 | 上海固钛实业有限公司 | Preparation method of citric acid |
| CN112409167A (en) * | 2020-11-27 | 2021-02-26 | 日照金禾博源生化有限公司 | Preparation method of calcium citrate whisker |
| CN114573442A (en) * | 2020-11-30 | 2022-06-03 | 南通星辰合成材料有限公司 | Treatment method of reaction waste liquid in polyphenyl ether synthesis process |
| CN114573442B (en) * | 2020-11-30 | 2024-05-24 | 南通星辰合成材料有限公司 | Treatment method of reaction waste liquid in polyphenyl ether synthesis process |
| CN115212815A (en) * | 2022-08-13 | 2022-10-21 | 山东巨展新材料有限公司 | Preparation method of water-soluble citric acid colloid |
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