CN102241584A - Production method of calcium hydrogen citrate - Google Patents
Production method of calcium hydrogen citrate Download PDFInfo
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- CN102241584A CN102241584A CN2011101172942A CN201110117294A CN102241584A CN 102241584 A CN102241584 A CN 102241584A CN 2011101172942 A CN2011101172942 A CN 2011101172942A CN 201110117294 A CN201110117294 A CN 201110117294A CN 102241584 A CN102241584 A CN 102241584A
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Abstract
The invention provides a production method of calcium hydrogen citrate. The method comprises the following steps of: continually mixing a citric acid fermentation clear solution, a calcium carbonate serum and a flaky calcium hydrogen citrate seed crystal; and undergoing a reaction under the condition of transforming citric acid in the citric acid fermentation clear solution into calcium hydrogen citrate crystals. Due to the adoption of the method, solid-liquid separation of the calcium hydrogen citrate crystals is facilitated, the using amount of washing water is reduced during water washing, the readily carbonization times of the calcium hydrogen citrate are lowered, the purity of the calcium hydrogen citrate is increased, and high-quality calcium hydrogen citrate crystals can be obtained.
Description
Technical field
The present invention relates to a kind of production method of hydrogen citrate calcium.
Background technology
Citric acid is a kind of organic acid that is widely used in industries such as beverage, food and medicine, the preparation method of citric acid generally comprises: raw material is carried out pre-treatment and ferment obtaining the citric acid fermentation clear liquid, and further purifying citric acid from fermentation clear liquid, and carry out aftertreatment.The method of purifying citric acid from fermentation clear liquid of prior art comprises calcium salt method, hydrogen calcium method and chromatography, because chromatography is carried out pre-treatment to material step more complicated, and the off-set facility investment is higher, and calcium salt method that general common employing is more traditional or hydrogen calcium method are purified to the citric acid that fermentation obtains.
Generally, hydrogen calcium method purifying citric acid comprises that elder generation generates citrate of lime with citric acid fermentation clear liquid and calcium carbonate serosity reaction, is that starting raw material prepares hydrogen citrate calcium then with the citrate of lime.It is longer to adopt existing method to prepare production process residence time of hydrogen citrate calcium, and the granularity of the hydrogen citrate calcium crystal grain that obtains is less than normal, granular size is inhomogeneous, therefore, in the time will containing hydrogen citrate calcium crystalline slurries and carry out follow-up filtration treatment, be difficult to hydrogen citrate calcium crystal grain is separated from slurries fully, and, when the hydrogen citrate calcium crystal that obtains is washed, can occur cleaning and thoroughly to cause the problem that leaching requirement increases, hydrogen citrate calcium purity is low.
Goal of the invention
Goal of the invention of the present invention is when overcoming the method production hydrogen citrate calcium that adopts prior art, less than normal owing to the hydrogen citrate calcium crystal grain granularity that obtains, granular size is inhomogeneous causes being difficult to hydrogen citrate calcium crystal grain is separated from slurries fully, and when washing leaching requirement increase, defective that hydrogen citrate calcium purity is low, provide a kind of hydrogen citrate calcium crystal grain that can be easy to separate and obtain big and evenly and the production method of the higher hydrogen citrate calcium of purity.
The invention provides a kind of production method of hydrogen citrate calcium, wherein, this method comprises mixes citric acid fermentation clear liquid, calcium carbonate serosity and sheet hydrogen citrate calcium crystal seed and reaction continuously, and the condition of reaction makes the citric acid in this citric acid fermentation clear liquid be converted into hydrogen citrate calcium crystal.
The method of the production hydrogen citrate calcium of prior art normally utilizes the method for nature graining when hydrogen citrate calcium slurries reach certain saturation concentration to carry out crystallization, therefore the crystal grain that generates is less, and be easy to take place sudden and violent brilliant phenomenon, promptly, a plurality of little grain colonies are got together, form the druse particle, thereby influenced the quality of hydrogen citrate calcium crystal product.And the present inventor finds, with the citric acid fermentation clear liquid, degree of supersaturation when continuous mixing of calcium carbonate serosity and sheet hydrogen citrate calcium crystal seed and reaction can reduce crystallization, shortened inductive phase, effectively avoided sudden and violent brilliant problem, and the hydrogen citrate calcium crystalline particle that finally obtains is big and even, in addition, adopt method of the present invention to help hydrogen citrate calcium crystalline solid-liquid separation, and when washing, reduced the consumption of wash water, reduced the easy charcoal multiple of hydrogen citrate calcium, improve the purity of hydrogen citrate calcium, thereby can access high-quality hydrogen citrate calcium crystal.
In addition, under the preferable case, the hydrogen citrate mother liquor of calcium conversion that obtains after the solid-liquid separation is obtained citrate of lime, and with citrate of lime when mixing with calcium carbonate serosity and hydrogen citrate calcium crystal seed again after the citric acid fermentation clear liquid mixes, owing to when initial reaction, added hydrogen citrate calcium crystal seed, thereby help the transformation of citrate of lime to hydrogen citrate calcium, reduced the reaction required time, can reduce the double team of citrate of lime in the hydrogen citrate calcium, obtain the big and uniform regular flaky hydrogen citrate calcium crystal of particle thereby be beneficial to more.
Description of drawings
Fig. 1 is hydrogen citrate calcium crystalline technological process of production figure provided by the invention;
Fig. 2 is the electromicroscopic photograph of the citrate of lime crystal product that adopts method of the present invention and obtain;
The electromicroscopic photograph of the citrate of lime crystal product that Fig. 3 obtains for the method that adopts prior art.
Embodiment
According to the present invention, the production method of described hydrogen citrate calcium comprises mixes citric acid fermentation clear liquid, calcium carbonate serosity and sheet hydrogen citrate calcium crystal seed and reaction continuously, and the condition of reaction makes the citric acid in this citric acid fermentation clear liquid be converted into hydrogen citrate calcium crystal.Although promptly can reach purpose of the present invention as long as add hydrogen citrate calcium crystal seed, promptly can prevent sudden and violent brilliant phenomenon on the one hand, can be beneficial to crystallization on the other hand and obtain the big and uniform hydrogen citrate calcium crystal of particle, but, under the preferable case, the particle diameter of the sheet hydrogen citrate calcium crystal seed that control adds is 0.08-0.15mm, and more preferably 0.09-0.12mm can further be beneficial to the crystallization of hydrogen citrate calcium.
In the present invention, can guarantee to make the citric acid crystalline particle that obtains big and even as long as guarantee when hybrid reaction, to add sheet citric acid crystal seed, therefore, the present invention is not particularly limited the condition of mixing and react, but, under the preferable case, in order to be more conducive to the crystallization of hydrogen citrate calcium, the condition of described mixing and reaction can comprise endpoint pH and the temperature and time that mixes and react.The terminal point pH that preferably makes described mixing and reaction is 2.5-3.5, and 2.8-3.1 more preferably can guarantee in this pH value scope that promptly crystalline is shaped and separates out; For crystal is fully grown up, the temperature of described mixing and reaction is preferably 50-90 ℃, more preferably 65-80 ℃; Mix and reaction total time can be 1-8 hour, be preferably 1-6 hour.
According to the present invention, continuous mixing of citric acid fermentation clear liquid, calcium carbonate serosity and sheet hydrogen citrate calcium crystal seed and reaction can be carried out in a mixed reactor, also can in a plurality of mixed reactors, carry out, under the preferable case, for the control that is beneficial to condition more and be convenient to operate continuously, according to a concrete embodiment of the present invention, the continuous method of mixing and reacting of citric acid fermentation clear liquid, calcium carbonate serosity and hydrogen citrate calcium crystal seed is comprised:
(1) citric acid fermentation clear liquid, calcium carbonate serosity and sheet hydrogen citrate calcium crystal seed are joined continuously in the mixing tank and to mix 1-2 hour;
(2) reaction mixture that step (1) is obtained moved at least one crystallizer sustained reaction 2-6 hour, and the sheet hydrogen citrate calcium crystalline slurries that contain that obtain are carried out solid-liquid separation, obtained sheet hydrogen citrate calcium crystal and hydrogen citrate mother liquor of calcium.
According to the present invention, the sheet citric acid crystal seed in the described step (1) can be a sheet hydrogen citrate calcium crystal seed arbitrarily, and being preferably particle diameter is 0.08-0.15mm, more preferably the sheet hydrogen citrate calcium crystal seed of 0.09-0.12mm.In addition, described sheet hydrogen citrate calcium crystal seed can be the crystal seed that adds, and also can be the crystal seed from other technologies.Under the preferable case, in order to be more conducive to carrying out continuously of hydrogen citrate calcium crystalline production technique, described sheet hydrogen citrate calcium crystal seed is the sheet hydrogen citrate calcium crystal that step (2) obtains.
According to the present invention, the mixing temperature of described step (1) can be 50-90 ℃, and endpoint pH can be 2.5-3; The temperature of reaction of step (2) can be 50-90 ℃, and endpoint pH can be 3-3.5.For more accurate control reaction conditions, be beneficial to crystalline and carry out, the mixing temperature of step (1) can be 65-80 ℃, endpoint pH can be 2.6-2.9; The temperature of reaction of step (2) can be 65-80 ℃, and endpoint pH can be 2.9-3.1.
According to the present invention, for the ease of crystallization better, the number of described crystallizer generally is preferably 2-5, and more preferably 2-3, a plurality of crystallizers are connected in series, and the reaction times in each crystallizer generally can be 1-2 hour.
According to the present invention, the selectable range broad of the ratio of described citric acid fermentation clear liquid and calcium carbonate serosity under the preferable case, is taken all factors into consideration cost and quality, and the mol ratio of citric acid and lime carbonate can be 1: 0.6-1, more preferably 1: 0.7-0.9.
According to the present invention, the selectable range broad of the addition of described hydrogen citrate calcium crystal seed, as long as promptly can realize the present invention although added described hydrogen citrate calcium crystal seed, but, more preferably under the situation, the citric acid fermentation clear liquid is 1 with weight ratio in the sheet hydrogen citrate calcium crystal seed of butt: 0.005-0.05, more preferably 1: 0.007-0.04.
As mentioned above, in order to realize the continuity of technology, the sheet hydrogen citrate calcium crystal that step (2) can be obtained is as sheet hydrogen citrate calcium crystal seed to be added, is about to the operation that hydrogen citrate calcium crystal that step (2) obtains returns repeating step (1) in the step (1) and gets final product.In addition, the present invention does not have special requirement to the form of described hydrogen citrate calcium crystal seed, that is to say that described sheet hydrogen citrate calcium crystal seed can add in the form of the sheet hydrogen citrate calcium crystal seed of butt, also can add with the form of the slurries that contain described sheet hydrogen citrate calcium crystal seed.The described hydrogen citrate calcium crystalline amount of returning is not particularly limited, and under the preferable case, its addition is as long as preferably guarantee in above-mentioned citric acid fermentation clear liquid and proportional range in the sheet hydrogen citrate calcium crystal seed of butt.Find through experiment, under the preferable case, the 10-50 weight % of the gross weight that contains sheet hydrogen citrate calcium crystalline slurries that step (2) is obtained, more preferably the 15-25 weight % of gross weight returns and promptly can satisfy aforementioned proportion requirement (the described wet solid content that contains sheet hydrogen citrate calcium crystalline slurries is generally 20-30 weight %, and wherein wet solid water branch is generally 60-65 weight %) in the step (1).
According to the present invention, this method also comprises the hydrogen citrate mother liquor of calcium transformed and obtains citrate of lime, and the citrate of lime that obtains is mixed back the adding in the mixing tank continuously with calcium carbonate serosity and sheet hydrogen citrate calcium crystal seed mix with the citric acid fermentation clear liquid of step (1), to improve the yield of product.Wherein, the hydrogen citrate mother liquor of calcium is transformed the method that obtains citrate of lime can be any method known in those skilled in the art, for example, hydrogen citrate mother liquor of calcium and calcium carbonate reaction are obtained citrate of lime, the endpoint pH of reaction can be 4.8-5.1, the temperature of reaction can be 60-90 ℃, and the time of reaction can be 1-2 hour.
According to the present invention, the adding of hydrogen citrate calcium crystal seed helps the formation of hydrogen citrate calcium, has reduced the reaction required time, can reduce the double team of citrate of lime in the hydrogen citrate calcium; Can obtain simultaneously big, the uniform hydrogen citrate calcium crystal of granularity, help the solid-liquid separation of hydrogen citrate calcium, reduce the easy charcoal multiple of hydrogen citrate calcium, obtain high-quality hydrogen citrate calcium crystal.
According to the present invention, because the adding of citrate of lime is in order to reclaim the hydrogen citrate calcium in the hydrogen citrate mother liquor of calcium, to improve the yield of hydrogen citrate calcium crystal product, therefore, the addition of described citrate of lime can be very not big, and be not particularly limited.Under the preferable case, described citric acid fermentation clear liquid can be 1 with the weight ratio that is transformed the citrate of lime that obtains by the hydrogen citrate mother liquor of calcium: 0.1-0.3 is preferably 1: 0.1-0.25.
The present invention is not particularly limited the concentration of calcium carbonate serosity, as long as guarantee to make lime carbonate and citric acid reactions, under the preferable case, described calcium carbonate serosity is the calcium carbonate water slurries, and the solid content of suitable calcium carbonate serosity can be 30-50 weight %.
According to the present invention, this method also comprises washes the hydrogen citrate calcium crystal that obtains to remove the step of residual impurity.The method of described washing can well known to a person skilled in the art method and condition for employing.For example, wash hydrogen citrate calcium with the method for water wash or dipping.As long as the condition of washing and method are with the remaining impurities flush away.
As described in goal of the invention of the present invention, because the big and uniform particles of the hydrogen citrate calcium crystalline particle that adopts method of the present invention to obtain, therefore, be highly susceptible to solid-liquid separation, therefore, when the hydrogen citrate calcium crystal that obtains is washed, can significantly reduce the consumption of washing water, and improve its purity simultaneously.
In addition, owing to the solubleness of the solubleness of hydrogen citrate calcium in water much larger than citrate of lime, therefore, the consumption of washing water and the time of washing remove with the impurity that will remain in hydrogen citrate calcium surface as far as possible and are as the criterion.The present inventor finds, in order well to guarantee hydrogen citrate calcium remained on surface is removed, and can reduce solution loss again, and therefore, the consumption of described washing water preferably only promptly can achieve the above object for the 10-18% of fermentation clear liquid volume.The temperature of washing can be 60-90 ℃, more preferably 65-80 ℃ usually.
According to the present invention, the preparation method of described citric acid fermentation clear liquid can adopt and well known to a person skilled in the art that prepared in various methods obtains, for example, described preparation method comprises maize raw material is pulverized, the crushed products that obtains is liquefied, fermentation obtains the citric acid product, and the content of citric acid is generally the 100-120 gram in every liter of citric acid fermentation clear liquid.
Under the preferable case, this method before also being included in reaction is sterilized described citric acid fermentation clear liquid, and the condition of described sterilization can be the sterilising conditions of routine known in those skilled in the art, for example, the temperature that comprises sterilization can be 65-70 ℃, and the time of sterilization can be 10-20 minute.
As shown in Figure 1, according to a concrete preferred implementation of the present invention, described hydrogen citrate calcium crystalline production method comprises the steps:
(1) in the one-level crystallizer, adds simultaneously continuously citric acid fermentation clear liquid, calcium carbonate serosity and contain the slurries of sheet hydrogen citrate calcium crystal seed, mix and carry out reactive crystallization;
(2) behind reaction certain hour in the one-level crystallizer, material in the one-level crystallizer is carried toward the secondary crystallization jar;
(3) behind reaction certain hour in the secondary crystallization jar, the material in the secondary crystallization jar is carried toward three grades of crystallizers;
(4) behind reaction certain hour in three grades of crystallizers, the part slurry that contains sheet hydrogen citrate calcium crystal seed in three grades of crystallizers is as the hydrogen citrate calcium crystal seed in the step (1), add in the described one-level crystallizer, the remaining slurry that contains sheet hydrogen citrate calcium is carried out solid-liquid separation, obtain solid phase and hydrogen citrate mother liquor of calcium;
(5) wash the solid phase that step (4) obtains with water, obtain hydrogen citrate calcium crystal product;
(6) hydrogen citrate mother liquor of calcium and the calcium carbonate reaction that step (4) is obtained obtains citrate of lime, promptly as the reaction raw materials citrate of lime in the step (1).
To further describe in detail the present invention by specific embodiment below.
Used citric acid fermentation clear liquid makes by the following method among the following embodiment: 0.872 kg corn is pulverized with SFSP series beater disintegrating machine, and obtaining average particulate diameter is 0.871 kilogram of crushed products of 2 millimeters (adopting the Accu Sizer TM 780 optics particle diameter detectors of U.S. PPS company to measure); 83 ± 1 ℃ of liquefaction temperatures, 93 ± 1 ℃ of secondary liquefaction controlled temperature mix crushed products and to carry out steam ejection liquefaction with amylase, and holding time is 40-60 minute, and the pH value of described enzymolysis maintains 5.7-6.2; The α-Dian Fenmei 0.7g/kg Semen Maydis powder (Novozymes Company buys) of adding vigor 〉=2000u/ml; Temperature is reduced to 38 ℃, the inoculation biomass is the aspergillus niger of 18g/l (fermented liquid), the gained mixture under 37 ℃ in fermentor tank stir culture 65 hours, obtain the mix products that ferments, and filter and obtain 5 liters of citric acid fermentation clear liquids (content of citric acid is 110 grams in every liter of citric acid fermentation clear liquid).
Measure the easy charcoal multiple of hydrogen citrate calcium acid hydrolysis solution according to " foodstuff additive " citric acid GB1987-2007.
Embodiment 1
Present embodiment is used to illustrate the production method of hydrogen citrate calcium provided by the invention.
(1) the continuous simultaneously slurries that add citric acid fermentation clear liquid, calcium carbonate water slurries (solid content is 40 weight %) and contain sheet hydrogen citrate calcium crystal seed (particle diameter is 0.1mm) in the one-level crystallizer, mixing is also carried out reactive crystallization, the mole number of citrate and the mol ratio of lime carbonate are 1: 0.8, and the citric acid fermentation clear liquid is 1: 0.036 with weight ratio in the sheet hydrogen citrate calcium crystal seed of butt; Reaction end pH value is 3, and the temperature of reactive crystallization is 65 ℃, stirs all the time in the process and opens, and mixing time is 1.2 hours;
(2) one-level crystallizer liquid level reaches 500 liters when react 1.2 hours in the one-level crystallizer after, and material in the one-level crystallizer is carried toward the secondary crystallization jar, guarantees that simultaneously one-level crystallizer liquid level is controlled at 500 liters, and promptly the input and output material flow is identical; The reactive crystallization temperature of secondary crystallization jar is 68 ℃, and the reaction times is 1.2 hours, and reaction end pH value is 3.2;
(3) secondary crystallization jar liquid level reaches 500 liters when react 1.2 hours in the secondary crystallization jar after, material in the secondary crystallization jar is carried toward three grades of crystallizers, guarantee that simultaneously secondary crystallization jar liquid level is controlled at 500 liters, promptly the input and output material flow is identical, stirs all the time in the process and opens; The reactive crystallization temperature of three grades of crystallizers is 68 ℃, and the reaction times is 1.2 hours, and reaction end pH value is 3.2;
(4) after in three grades of crystallizers, reacting 1.2 hours, three grades of crystallizer liquid levels reach 500 liters, hydrogen citrate calcium crystal seed in the step (1) is for the sheet hydrogen citrate calcium crystalline part slurry of containing in three grades of crystallizers being provided provide in the one-level crystallizer, (the wet solid content of sheet hydrogen citrate calcium crystal seed is 30 weight % to the weight of the part slurry that adds in the described slurry for about 20 weight % of slurry gross weight in this crystallizer, wet solid water is divided into 60 weight %), the remaining sheet hydrogen citrate calcium crystalline slurry that contains is entered and carries out solid-liquid separation in the conveyor drive, obtain solid phase and hydrogen citrate mother liquor of calcium; Guarantee that simultaneously three grades of crystallizer liquid levels are controlled at 500 liters, promptly the input and output material flow is identical;
(5) (the wash water temperature is 70 ℃ to wash the solid phase that step (4) obtains with water, the consumption of water is 17 weight % of citric acid fermentation clear liquid weight), obtain hydrogen citrate calcium crystal product, this hydrogen citrate calcium crystal product amplify 600 times electromicroscopic photograph as shown in Figure 2, citric acid hydrogen calcium product parameter is as shown in table 1.
Comparative Examples 1
This Comparative Examples is used to illustrate the reference production method of hydrogen citrate calcium.
(1) in the one-level crystallizer, adds citric acid fermentation clear liquid and calcium carbonate water slurries (solid content is 40 weight %) simultaneously continuously, mixing is also carried out reactive crystallization, the mole number of citrate and the mol ratio of lime carbonate are 1: 0.8, control reaction end pH value is 3, the temperature of reactive crystallization is 65 ℃, stir all the time in the process and open, mixing time is 1.2 hours;
(2) one-level crystallizer liquid level reaches 500 liters when react 1.2 hours in the one-level crystallizer after, and material in the one-level crystallizer is carried toward the secondary crystallization jar, guarantees that simultaneously one-level crystallizer liquid level is controlled at 500 liters, and promptly the input and output material flow is identical; The reactive crystallization temperature of secondary crystallization jar is 68 ℃, and the reaction times is 1.2 hours, and control reaction end pH value is 3.2;
(3) secondary crystallization jar liquid level reaches 500 liters when react 1.2 hours in the secondary crystallization jar after, material in the secondary crystallization jar is carried toward three grades of crystallizers, guarantee that simultaneously secondary crystallization jar liquid level is controlled at 500 liters, promptly the input and output material flow is identical, stirs all the time in the process and opens; The reactive crystallization temperature of three grades of crystallizers is 68 ℃, and the reaction times is 1.2 hours, and control reaction end pH value is 3.2;
(4) when reaction is after 1.2 hours in three grades of crystallizers, three grades of crystallizer liquid levels reach 500 liters, will contain hydrogen citrate calcium crystalline slurry and enter and carry out solid-liquid separation in the conveyor drive, obtain solid phase and hydrogen citrate mother liquor of calcium; Guarantee that simultaneously three grades of crystallizer liquid levels are controlled at 500 liters, promptly the input and output material flow is identical;
(5) (the wash water temperature is 70 ℃ to wash the solid phase that step (4) obtains with water, the consumption of water is 20 weight % of citric acid fermentation clear liquid weight), obtain hydrogen citrate calcium crystal product, this hydrogen citrate calcium crystal product amplify 600 times electromicroscopic photograph as shown in Figure 3, citric acid hydrogen calcium product parameter is as shown in table 1.
Embodiment 2
Present embodiment is used to illustrate the production method of hydrogen citrate calcium provided by the invention.
Method according to embodiment 1 prepares hydrogen citrate calcium, different is, this method also is included under 70 ℃, with hydrogen citrate mother liquor of calcium and the calcium carbonate reaction that obtains, the pH value of reaction end is 5, reaction times is 1 hour, obtains citrate of lime, and citrate of lime mixed with the citric acid fermentation clear liquid of step (1) and joins hybrid reaction in the crystallizer continuously with calcium carbonate serosity and the slurries that contain sheet hydrogen citrate calcium crystal seed; The weight ratio of citric acid fermentation clear liquid and citrate of lime is 1: 0.1.
Embodiment 3
Present embodiment is used to illustrate the production method of hydrogen citrate calcium provided by the invention.
(1) the continuous simultaneously slurries that add citric acid fermentation clear liquid, calcium carbonate water slurries (solid content is 48 weight %), citrate of lime and contain sheet hydrogen citrate calcium crystal seed (particle diameter is 0.12mm) in the one-level crystallizer, mixing is also carried out reactive crystallization, the mol ratio of the mole number of citrate and lime carbonate is 1: 0.9 in the mixture, and the weight ratio of citric acid fermentation clear liquid and citrate of lime is 1: 0.25; The citric acid fermentation clear liquid is 1: 0.025 with weight ratio in the sheet hydrogen citrate calcium crystal seed of butt; Reaction end pH is 2.8, and the temperature of reactive crystallization is 70 ℃, stirs all the time in the process and opens, and the reaction times is 1 hour.
(2) one-level crystallizer liquid level reaches 500 liters when react 1 hour in the one-level crystallizer after, and material in the one-level crystallizer is carried toward second stage crystallizer, guarantees that simultaneously first step crystallizer liquid level is controlled at 500 liters, and promptly the input and output material flow is identical; The reactive crystallization temperature of secondary crystallization jar is 72 ℃, and the reaction times is 1 hour, and reaction end pH value is 2.9;
(3) secondary crystallization jar liquid level reaches 500 liters when react 1 hour in the secondary crystallization jar after, material in the secondary crystallization jar is carried toward three grades of crystallizers, guarantee that simultaneously secondary crystallization jar liquid level is controlled at 500 liters, be that the input and output material flow is identical, the reactive crystallization temperature is 72 ℃, reaction times is 1 hour, stirs all the time in the process and opens, and reaction end pH value is 3.0;
(4) three grades of crystallizer liquid levels reach 500 liters when react 1 hour in three grades of crystallizers after, hydrogen citrate calcium crystal seed in the step (1) is for the sheet hydrogen citrate calcium crystalline part slurry of containing in three grades of crystallizers being provided provide in the one-level crystallizer, (the wet solid content of sheet hydrogen citrate calcium crystal seed is 30 weight % to the weight of the part slurry that adds in the described slurry for about 16 weight % of slurry gross weight in this crystallizer, wet solid water is divided into 60 weight %), the remaining sheet hydrogen citrate calcium crystalline slurry that contains is entered and carries out solid-liquid separation in the conveyor drive, obtain solid phase and hydrogen citrate mother liquor of calcium; Guarantee that simultaneously three grades of crystallizer liquid levels are controlled at 500 liters, promptly the input and output material flow is identical;
(5) wash the solid phase (the wash water temperature is 75 ℃, and the consumption of water is 14 weight % of citric acid clear liquid weight) that step (4) obtains with water, obtain hydrogen citrate calcium crystal product;
(6) under 80 ℃, with hydrogen citrate mother liquor of calcium and the calcium carbonate reaction that step (4) obtains, the pH value of reaction end is 4.9, and the reaction times is 0.8 hour, obtains citrate of lime, promptly as the reaction raw materials citrate of lime in the step (1).
Embodiment 4
Present embodiment is used to illustrate the production method of hydrogen citrate calcium provided by the invention.
(1) the continuous simultaneously slurries that add citric acid clear liquid, calcium carbonate water slurries (solid content is 45 weight %), citrate of lime and contain sheet hydrogen citrate calcium crystal seed (particle diameter is 0.08mm) in the one-level crystallizer, mixing is also carried out reactive crystallization, the mol ratio of the mole number of citrate and lime carbonate is 1: 0.7 in the mixture, and the weight ratio of citric acid fermentation clear liquid and citrate of lime is 1: 0.1; The citric acid fermentation clear liquid is 1: 0.012 with weight ratio in the sheet hydrogen citrate calcium crystal seed of butt; Reaction end pH value is 2.9, and the temperature of reactive crystallization is 75 ℃, stirs all the time in the process and opens, and the reaction times is 1.5 hours;
(2) one-level crystallizer liquid level reaches 500 liters when react 1.5 hours in the one-level crystallizer after, and material in the one-level crystallizer is carried toward second stage crystallizer, guarantees that simultaneously first step crystallizer liquid level is controlled at 500 liters, and promptly the input and output material flow is identical; The reactive crystallization temperature of secondary crystallization jar is 79 ℃, and the reaction times is 1.5 hours, and reaction end pH value is 3.0;
(3) secondary crystallization jar liquid level reaches 500 liters when react 1.5 hours in the secondary crystallization jar after, material in the secondary crystallization jar is carried toward three grades of crystallizers, guarantee that simultaneously secondary crystallization jar liquid level is controlled at 500 liters, be that the input and output material flow is identical, the reactive crystallization temperature is 80 ℃, reaction times is 1.5 hours, stirs all the time in the process and opens, and reaction end pH value is 3.1;
(4) three grades of crystallizer liquid levels reach 500 liters when react 1.5 hours in three grades of crystallizers after, hydrogen citrate calcium crystal seed in the step (1) is for the sheet hydrogen citrate calcium crystalline part slurry of containing in three grades of crystallizers being provided provide in the one-level crystallizer, (the wet solid content of sheet hydrogen citrate calcium crystal seed is 30 weight % to the weight of the part slurry that adds in the described slurry for about 13 weight % of slurry gross weight in this crystallizer, wet solid water is divided into 60 weight %), the remaining sheet hydrogen citrate calcium crystalline slurry that contains is entered and carries out solid-liquid separation in the conveyor drive, obtain solid phase and hydrogen citrate mother liquor of calcium; Guarantee that simultaneously three grades of crystallizer liquid levels are controlled at 500 liters, promptly the input and output material flow is identical;
(5) wash the solid phase (the wash water temperature is 80 ℃, and the consumption of water is 15 weight % of citric acid clear liquid weight) that step (4) obtains with water, obtain hydrogen citrate calcium crystal product;
(6) under 65 ℃, with hydrogen citrate mother liquor of calcium and the calcium carbonate reaction that step (4) obtains, the pH value of reaction end is 4.8, and the reaction times is 0.6 hour, obtains citrate of lime, promptly as the reaction raw materials citrate of lime in the step (1).
Embodiment 5
Present embodiment is used to illustrate the production method of hydrogen citrate calcium provided by the invention.
(1) the continuous simultaneously slurries that add citric acid clear liquid, calcium carbonate water slurries (solid content is 40 weight %), citrate of lime and contain sheet hydrogen citrate calcium crystal seed (particle diameter is 0.09mm) in the one-level crystallizer, mixing is also carried out reactive crystallization, the mol ratio of the mole number of citrate and lime carbonate is 1: 0.5 in the mixture, and the weight ratio of citric acid fermentation clear liquid and citrate of lime is 1: 0.25; The citric acid fermentation clear liquid is 1: 0.0045 with weight ratio in the sheet hydrogen citrate calcium crystal seed of butt; Reaction end pH value is 2.7, and the temperature of reactive crystallization is 75 ℃, stirs all the time in the process and opens, and the reaction times is 1.5 hours;
(2) one-level crystallizer liquid level reaches 500 liters when react 1.2 hours in the one-level crystallizer after, and material in the one-level crystallizer is carried toward second stage crystallizer, guarantees that simultaneously first step crystallizer liquid level is controlled at 500 liters, and promptly the input and output material flow is identical; The reactive crystallization temperature of secondary crystallization jar is 75 ℃, and the reaction times is 1.5 hours, and reaction end pH value is 2.9;
(3) secondary crystallization jar liquid level reaches 500 liters when react 1.5 hours in the secondary crystallization jar after, material in the secondary crystallization jar is carried toward three grades of crystallizers, guarantee that simultaneously secondary crystallization jar liquid level is controlled at 500 liters, be that the input and output material flow is identical, the reactive crystallization temperature is 75 ℃, reaction times is 1.5 hours, stirs all the time in the process and opens, and reaction end pH value is 3.0;
(4) three grades of crystallizer liquid levels reach 500 liters when react 1.5 hours in three grades of crystallizers after, hydrogen citrate calcium crystal seed in the step (1) is for the sheet hydrogen citrate calcium crystalline part slurry of containing in three grades of crystallizers being provided provide in the one-level crystallizer, (the wet solid content of sheet hydrogen citrate calcium crystal seed is 30 weight % to the weight of the part slurry that adds in the described slurry for about 12 weight % of slurry gross weight in this crystallizer, wet solid water is divided into 60 weight %), the remaining slurry that contains sheet hydrogen citrate calcium crystal seed entered carry out solid-liquid separation in the conveyor drive, obtain solid phase and hydrogen citrate mother liquor of calcium; Guarantee that simultaneously three grades of crystallizer liquid levels are controlled at 500 liters, promptly the input and output material flow is identical;
(5) wash the solid phase (the wash water temperature is 80 ℃, and the consumption of water is 16 weight % of citric acid clear liquid weight) that step (4) obtains with water, obtain hydrogen citrate calcium crystal product;
(6) under 80 ℃, with hydrogen citrate mother liquor of calcium and the calcium carbonate reaction that step (4) obtains, the pH value of reaction end is 4.9, and the reaction times is 1 hour, obtains citrate of lime, promptly as the reaction raw materials citrate of lime in the step (1).
Embodiment 6
Present embodiment is used to illustrate the production method of hydrogen citrate calcium provided by the invention.
(1) the continuous simultaneously slurries that add citric acid clear liquid, calcium carbonate water slurries (solid content is 50 weight %), citrate of lime and contain sheet hydrogen citrate calcium crystal seed (particle diameter is 0.15mm) in the one-level crystallizer, mixing is also carried out reactive crystallization, the mol ratio of the mole number of citrate and lime carbonate is 1: 1 in the mixture, and the weight ratio of citric acid fermentation clear liquid and citrate of lime is 1: 0.25; The citric acid fermentation clear liquid is 1: 0.052 with weight ratio in the sheet hydrogen citrate calcium crystal seed of butt; Reaction end pH value is 2.9, and the temperature of reactive crystallization is 75 ℃, stirs all the time in the process and opens, and the reaction times is 1.5 hours;
(2) one-level crystallizer liquid level reaches 500 liters when react 1.5 hours in the one-level crystallizer after, and material in the one-level crystallizer is carried toward second stage crystallizer, guarantees that simultaneously first step crystallizer liquid level is controlled at 500 liters, and promptly the input and output material flow is identical; The reactive crystallization temperature of secondary crystallization jar is 75 ℃, and the reaction times is 1.5 hours, and reaction end pH value is 3.1;
(3) secondary crystallization jar liquid level reaches 500 liters when react 1.5 hours in the secondary crystallization jar after, material in the secondary crystallization jar is carried toward three grades of crystallizers, guarantee that simultaneously secondary crystallization jar liquid level is controlled at 500 liters, be that the input and output material flow is identical, the reactive crystallization temperature is 75 ℃, reaction times is 1.5 hours, stirs all the time in the process and opens, and reaction end pH value is 3.1;
(4) three grades of crystallizer liquid levels reach 500 liters when react 1.5 hours in three grades of crystallizers after, hydrogen citrate calcium crystal seed in the step (1) is for the sheet hydrogen citrate calcium crystalline part slurry of containing in three grades of crystallizers being provided provide in the one-level crystallizer, (the wet solid content of sheet hydrogen citrate calcium crystal seed is 30 weight % to the weight of the part slurry that adds in the described slurry for about 25 weight % of slurry gross weight in this crystallizer, wet solid water is divided into 60 weight %), the remaining sheet hydrogen citrate calcium crystalline slurry that contains is entered and carries out solid-liquid separation in the conveyor drive, obtain solid phase and hydrogen citrate mother liquor of calcium; Guarantee that simultaneously three grades of crystallizer liquid levels are controlled at 500 liters, promptly the input and output material flow is identical;
(5) wash the solid phase (the wash water temperature is 80 ℃, and the consumption of water is 15 weight % of citric acid clear liquid weight) that step (4) obtains with water, obtain hydrogen citrate calcium crystal product;
(6) under 65 ℃, with hydrogen citrate mother liquor of calcium and the calcium carbonate reaction that step (4) obtains, the pH value of reaction end is 4.9, and the reaction times is 0.6 hour, obtains citrate of lime, promptly as the reaction raw materials citrate of lime in the step (1).
Table 1
The hydrogen citrate calcium crystalline granular size that adopts method of the present invention to obtain as can be seen from the contrast of Fig. 1 and Fig. 2 is big, even, and shape is regular, and the hydrogen citrate calcium crystalline granular size that the method that adopts prior art obtains is less, inhomogeneous, and the shape irregularity.From last table 1 be data as can be seen, the hydrogen citrate calcium that adopts method of the present invention to obtain, the leaching requirement during washing is obviously less, and the easy charcoal multiple of hydrogen citrate calcium acid hydrolysis solution is lower; Wherein what of readily carbonizable substance content in the hydrogen citrate calcium finished product the easy charcoal multiple of hydrogen citrate calcium acid hydrolysis solution directly influence, the easy charcoal multiple of lemon acid hydrogen calcium acid hydrolysis solution is directly proportional with the readily carbonizable substance content in the hydrogen citrate calcium finished product, and readily carbonizable substance is an important quality index of final product quality, adopt the easy charcoal multiple of acid hydrolysis solution of the hydrogen citrate calcium that method of the present invention obtains lower, illustrate that the readily carbonizable substance content in the hydrogen citrate calcium finished product that obtains is less, therefore, quality product is better.
Claims (14)
1. the production method of a hydrogen citrate calcium, it is characterized in that, this method comprises mixes citric acid fermentation clear liquid, calcium carbonate serosity and sheet hydrogen citrate calcium crystal seed and reaction continuously, and the condition of reaction makes the citric acid in this citric acid fermentation clear liquid be converted into hydrogen citrate calcium crystal.
2. method according to claim 1, wherein, the particle diameter of described hydrogen citrate calcium crystal seed is 0.08-0.15mm.
3. method according to claim 1, wherein, the condition of mixing and reaction comprises that the pH value of reaction end is 2.5-3.5, and the temperature of mixing and reaction is 50-90 ℃, and the total time of mixing and reaction is 1-8 hour.
4. method according to claim 3, wherein, the condition of mixing and reaction comprises that the pH value of reaction end is 2.6-3.1, and the temperature of mixing and reaction is 65-80 ℃, and the total time of mixing and reaction is 1-6 hour.
5. according to any described method among the claim 1-4, wherein, this method comprises:
(1) citric acid fermentation clear liquid, calcium carbonate serosity and sheet hydrogen citrate calcium crystal seed are joined continuously in the mixing tank and to mix 1-2 hour;
(2) reaction mixture that step (1) is obtained moved at least one crystallizer sustained reaction 2-6 hour, and the sheet hydrogen citrate calcium crystalline slurries that contain that obtain are carried out solid-liquid separation, obtained sheet hydrogen citrate calcium crystal and hydrogen citrate mother liquor of calcium.
6. method according to claim 5, wherein, sheet hydrogen citrate calcium crystal seed is the sheet hydrogen citrate calcium crystal that step (2) obtains.
7. method according to claim 5, wherein, the mixing temperature of step (1) is 50-90 ℃, endpoint pH is 2.5-3; The temperature of reaction of step (2) is 50-90 ℃, and endpoint pH is 3-3.5.
8. method according to claim 7, wherein, the mixing temperature of step (1) is 65-80 ℃, endpoint pH is 2.6-2.9; The temperature of reaction of step (2) is 65-80 ℃, and endpoint pH is 2.9-3.1.
9. method according to claim 5, wherein, the number of described crystallizer is 2-5, and a plurality of crystallizers are connected in series, and the reaction times in each crystallizer is 1-2 hour.
10. method according to claim 5, wherein, the mol ratio of citric acid and lime carbonate is 1: 0.6-1, the citric acid fermentation clear liquid is 1 with weight ratio in the sheet hydrogen citrate calcium crystal seed of butt: 0.005-0.05.
11. method according to claim 5, wherein, this method also comprises the hydrogen citrate mother liquor of calcium transformed and obtains citrate of lime, and the citrate of lime that obtains mixed with the citric acid fermentation clear liquid of step (1) afterwards to add in the mixing tank continuously with calcium carbonate serosity and sheet hydrogen citrate calcium crystal seed mix.
12. method according to claim 11, wherein, the weight ratio of citric acid fermentation clear liquid and citrate of lime is 1: 0.1-0.3.
13. method according to claim 5, wherein, this method also comprises washes the sheet hydrogen citrate calcium crystal that obtains, and the consumption of washing water is that the temperature that the 10-18% of the volume of citric acid fermentation clear liquid washes is 60-90 ℃.
14. method according to claim 5, wherein, the content of citric acid is the 100-120 gram in every liter of citric acid fermentation clear liquid; Described calcium carbonate serosity is the calcium carbonate water slurries, and the solid content of described calcium carbonate serosity is 30-50 weight %.
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Cited By (7)
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| CN102816059A (en) * | 2012-08-28 | 2012-12-12 | 中粮生物化学（安徽）股份有限公司 | Production method and application of calcium hydrogen citrate |
| CN103044239A (en) * | 2012-12-17 | 2013-04-17 | 日照金禾博源生化有限公司 | Production method of sodium citrate |
| CN103058853A (en) * | 2012-12-17 | 2013-04-24 | 日照金禾博源生化有限公司 | Method for producing calcium hydrogen citrate |
| CN105418411A (en) * | 2015-12-21 | 2016-03-23 | 日照金禾博源生化有限公司 | Preparation method for easily soluble calcium hydrogen citrate |
| CN105669428A (en) * | 2016-03-07 | 2016-06-15 | 江苏国信协联能源有限公司 | Production method of calcium hydrogen citrate |
| CN114085139A (en) * | 2021-10-27 | 2022-02-25 | 莱芜泰禾生化有限公司 | Method and device for continuous neutralization of citric acid neutralization tank |
| CN115572222A (en) * | 2022-08-11 | 2023-01-06 | 山东金禾保健品有限公司 | Preparation method and application of calcium citrate spherical crystal |
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| CN102816059A (en) * | 2012-08-28 | 2012-12-12 | 中粮生物化学（安徽）股份有限公司 | Production method and application of calcium hydrogen citrate |
| CN103044239A (en) * | 2012-12-17 | 2013-04-17 | 日照金禾博源生化有限公司 | Production method of sodium citrate |
| CN103058853A (en) * | 2012-12-17 | 2013-04-24 | 日照金禾博源生化有限公司 | Method for producing calcium hydrogen citrate |
| CN103044239B (en) * | 2012-12-17 | 2015-02-25 | 日照金禾博源生化有限公司 | Production method of sodium citrate |
| CN103058853B (en) * | 2012-12-17 | 2015-10-14 | 日照金禾博源生化有限公司 | A kind of production method of calcium hydrogen citrate |
| CN105418411A (en) * | 2015-12-21 | 2016-03-23 | 日照金禾博源生化有限公司 | Preparation method for easily soluble calcium hydrogen citrate |
| CN105669428A (en) * | 2016-03-07 | 2016-06-15 | 江苏国信协联能源有限公司 | Production method of calcium hydrogen citrate |
| CN105669428B (en) * | 2016-03-07 | 2018-06-01 | 江苏国信协联能源有限公司 | A kind of production method of calcium hydrogen citrate |
| CN114085139A (en) * | 2021-10-27 | 2022-02-25 | 莱芜泰禾生化有限公司 | Method and device for continuous neutralization of citric acid neutralization tank |
| CN114085139B (en) * | 2021-10-27 | 2023-12-01 | 莱芜泰禾生化有限公司 | Method and device for continuously neutralizing citric acid neutralization tank |
| CN115572222A (en) * | 2022-08-11 | 2023-01-06 | 山东金禾保健品有限公司 | Preparation method and application of calcium citrate spherical crystal |
| CN115572222B (en) * | 2022-08-11 | 2024-05-10 | 山东金禾保健品有限公司 | Preparation method and application of spherical calcium citrate crystal |
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