CN113861018B - Purification treatment method of citric acid mother liquor - Google Patents

Purification treatment method of citric acid mother liquor Download PDF

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CN113861018B
CN113861018B CN202111287031.6A CN202111287031A CN113861018B CN 113861018 B CN113861018 B CN 113861018B CN 202111287031 A CN202111287031 A CN 202111287031A CN 113861018 B CN113861018 B CN 113861018B
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citric acid
acid treatment
solution
heating
temperature
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CN113861018A (en
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齐圣
孟光兵
杜胜伟
时振
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Laiwu Taihe Biochemistry Co ltd
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Laiwu Taihe Biochemistry Co ltd
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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
    • 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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Abstract

The application relates to the field of citric acid mother liquor treatment, in particular to a purification treatment method of citric acid mother liquor; the method comprises the following steps: the method comprises the following steps: obtaining a citric acid mother solution; diluting the citric acid mother solution, and then adding an organic solvent to perform first heating to obtain a first citric acid treatment solution; adding disodium ethylenediamine tetraacetate into the first citric acid treatment solution, stirring and heating for the second time, and performing first heat preservation and first fine filtration to obtain a second citric acid treatment solution; adding an alkaline solution containing sodium into the second citric acid treatment solution, adjusting the pH, and then carrying out third temperature rising and second heat preservation to obtain a third citric acid treatment solution; cooling the third citric acid treatment liquid, and performing second fine filtration to obtain a fourth citric acid treatment liquid; and evaporating, concentrating and centrifuging the fourth citric acid treatment solution, and then decoloring and treating with cation exchange resin to obtain a pure sodium citrate solution.

Description

Purification treatment method of citric acid mother liquor
Technical Field
The application relates to the field of citric acid mother liquor treatment, in particular to a purification treatment method of citric acid mother liquor.
Background
Sodium citrate is an important citrate salt that can be used as a flavoring agent, stabilizer in the food and beverage industry; are used in the pharmaceutical industry as anti-coagulants, expectorants and diuretics; in the detergent industry, sodium tripolyphosphate can be replaced as an auxiliary agent of a nontoxic detergent; it is also used in brewing, injection, photographic medicine, electroplating, etc.
In the prior art, citric acid and alkaline solution containing sodium which are the main flows of the preparation method of the sodium citrate are subjected to neutralization reaction to prepare the sodium citrate, and citric acid is prepared by fermenting corn flour or tapioca flour generally, so that iron ion impurities are not dissolved in fermentation liquor of the citric acid, and meanwhile, polysaccharide, protein and other impurities exist in the fermentation liquor of the citric acid, and citric acid mother liquor is continuously generated in the reaction process of the citric acid and the alkaline solution.
The existing treatment method for the citric acid mother liquor comprises the steps of firstly reacting the generated citric acid mother liquor with calcium chloride to prepare calcium citrate, and then sequentially carrying out calcium salt separation, sugar washing, sulfuric acid hydrolysis, citric acid separation, carbon column decolorization, cation exchange and anion exchange to obtain the citric acid with better quality, so that the purification treatment of the citric acid is realized, but the process is complex, a large amount of wastewater is generated in each step, and therefore, how to simply purify the citric acid mother liquor is a technical problem to be solved in the present.
Disclosure of Invention
The application provides a purification treatment method of citric acid mother liquor, which aims at solving the technical problem that the treatment of the citric acid mother liquor is too complex in the prior art.
In a first aspect, the present application provides a method for purifying a citric acid mother liquor, the method comprising:
obtaining a citric acid mother solution;
diluting the citric acid mother solution, and then adding an organic solvent to perform first heating to obtain a first citric acid treatment solution;
adding disodium ethylenediamine tetraacetate into the first citric acid treatment solution, stirring and heating for the second time, and performing first heat preservation and first fine filtration to obtain a second citric acid treatment solution;
adding an alkaline solution containing sodium into the second citric acid treatment solution, adjusting the pH value, and then carrying out third temperature rising and second heat preservation to obtain a third citric acid treatment solution;
cooling the third citric acid treatment liquid, and performing second fine filtration to obtain a fourth citric acid treatment liquid;
and evaporating, concentrating and centrifuging the fourth citric acid treatment solution, and then decoloring and treating with cation exchange resin to obtain a pure sodium citrate solution.
Optionally, the mass ratio of the disodium ethylenediamine tetraacetate to the iron ions in the first citric acid treatment solution is 0.8-1.5.
Optionally, the alkaline solution containing sodium comprises at least one of sodium hydroxide, sodium carbonate and sodium bicarbonate.
Optionally, the end temperature of the first heating is 50-65 ℃, and the time of the first heating is 15-20 min;
the end temperature of the second heating is 75-85 ℃, and the time of the second heating is 15-20 min;
the final temperature of the third heating is 110-118 ℃, and the time of the third heating is 10-15 min.
Optionally, the first heat preservation includes: preserving heat for 20-25 min under the condition of the second temperature rising end point temperature;
the second insulation includes: and preserving heat for 15-20 min under the condition of the end temperature of the third heating.
Optionally, the end point pH of the pH adjustment is 7.5 to 8.5.
Optionally, the final temperature of the cooling is 50-65 ℃.
Optionally, the first fine filtration and the second fine filtration both comprise suction filtration under vacuum.
Optionally, the decoloring includes: and (3) decoloring through activated carbon adsorption, wherein the mass volume ratio of the activated carbon to the fourth citric acid treatment solution is 2 g/mL-5 g/mL.
Optionally, the water consumption for dilution is 1.5-2.5 times of the mass of the citric acid mother solution;
the evaporation amount of the evaporation concentration accounts for 15-20% of the volume of the fourth citric acid treatment liquid.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the purification treatment method for the citric acid mother solution, the citric acid mother solution is diluted, insoluble impurities are separated out, proteins are denatured and separated out through an organic solvent and first heating, impurities which are sensitive to solubility in the citric acid mother solution are primarily removed, chelating is carried out through disodium ethylenediamine tetraacetate, and because chelating is carried out in stirring, heavy metal cations are chelated to form aggregates, the second heating is carried out to accelerate the aggregation speed of the chelates, finally the chelates are completely aggregated in the third heating process, the first fine filtration is carried out to remove the chelates, the pH value of alkaline solution containing sodium is adjusted to convert citric acid and other impurity-difficult magazine acids into sodium salts, impurities which are sensitive to solubility in the sodium salts are removed through third heating, the impurities which are greatly affected by heating are removed through evaporation concentration and centrifugation, pigment molecules are removed through decolorization, and finally other impurity-difficult to-remove sodium citrate cations are treated through cation exchange resins, so that pure cation solution is obtained.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic flow chart of a method provided in an embodiment of the present application.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
In one embodiment of the present application, as shown in fig. 1, a method for purifying a citric acid mother solution, the method includes:
s1, obtaining a citric acid mother solution;
s2, diluting the citric acid mother solution, and then adding an organic solvent for first heating to obtain a first citric acid treatment solution;
s3, adding disodium ethylenediamine tetraacetate into the first citric acid treatment solution, stirring and heating for the second time, and performing first heat preservation and first fine filtration to obtain a second citric acid treatment solution;
s4, adding an alkaline solution containing sodium into the second citric acid treatment solution, adjusting the pH value, and then carrying out third temperature rise and second temperature preservation to obtain a third citric acid treatment solution;
s5, cooling the third citric acid treatment liquid, and performing second fine filtration to obtain a fourth citric acid treatment liquid;
s6, evaporating, concentrating and centrifuging the fourth citric acid treatment solution, and then decoloring and treating with cation exchange resin to obtain a pure sodium citrate solution;
wherein the organic solvent may be any one of ethanol, methanol and propanol.
As an alternative embodiment, the mass ratio of the disodium ethylenediamine tetraacetate to the iron ions in the first citric acid treatment solution is 0.8-1.5.
In the application, the mass ratio of the disodium ethylenediamine tetraacetate to the iron ions in the first citric acid treatment solution is limited to be 0.8-1.5, and the positive effects are that the iron ions and other impurity metal cations can be fully chelated to form an aggregate within the mass ratio range due to the fact that the iron ions in the citric acid mother solution are more; when the value of the mass ratio is larger than the end maximum value of the range, the adverse effect caused by excessive disodium ethylenediamine tetraacetate is that raw materials are wasted, new impurities are introduced, and when the value of the mass ratio is smaller than the end minimum value of the range, the adverse effect caused by insufficient disodium ethylenediamine tetraacetate content cannot remove iron ions and other impurity metal cations completely.
As an alternative embodiment, the alkaline solution containing sodium includes at least one of sodium hydroxide, sodium carbonate, and sodium bicarbonate.
In the application, the positive effect that the sodium-containing alkaline solution comprises at least one of sodium hydroxide, sodium carbonate and sodium bicarbonate is that the finally obtained product is sodium citrate, so that the pH value is adjusted through the sodium-containing sodium hydroxide, sodium carbonate and sodium bicarbonate solution, citric acid and other impurity acids in the citric acid mother solution are fully converted into sodium salts, and then the sodium salts are removed through subsequent treatment, so that the purification treatment of the citric acid mother solution is realized.
As an alternative embodiment, the end temperature of the first heating is 50-65 ℃, and the time of the first heating is 15-20 min;
the end temperature of the second heating is 75-85 ℃, and the time of the second heating is 15-20 min:
the final temperature of the third heating is 110-118 ℃, and the time of the third heating is 10-15 min.
In the application, the end temperature of the first heating is 50-65 ℃, and the positive effects are that in the temperature range, the citric acid mother liquor can be fully heated, so that protein impurities in the citric acid mother liquor after the organic solvent is added can be fully separated out, and a first citric acid treatment liquid without protein is obtained; when the value of the end point temperature is larger than the end point maximum value of the range, the adverse effect caused by the excessively high temperature is that the organic solvent is unstable, the organic solvent is volatilized, the protein is insufficiently precipitated, the protein treatment is affected, and when the value of the end point temperature is smaller than the end point minimum value of the range, the adverse effect caused by the excessively low temperature is that the denatured protein is insufficiently precipitated, and the subsequent treatment process is affected.
The positive effect of the first heating time being 15-20 min is that in the time range, protein can be fully precipitated, so that the first citric acid treatment liquid without protein is obtained; when the value of time is larger than the end maximum value of the range, the adverse effect caused by too long heating time is that the whole process time is prolonged, so that energy consumption is caused, and when the value of time is smaller than the end minimum value of the range, the adverse effect caused by too short heating time is that the protein is not sufficiently precipitated, so that the first citric acid treatment liquid without protein is not obtained.
The end temperature of the second heating is 75-85 ℃, and the positive effects are that in the temperature range, disodium ethylenediamine tetraacetate can be fully chelated with iron ions and other metal cations respectively to form chelate, and then the chelate is stirred to form agglomerates, so that a solution is separated out, and further a third citric acid treatment solution without metal cations can be obtained; when the temperature is greater than the end point maximum of the range, the adverse effect is that an excessively high temperature can increase the precipitation speed of the agglomerate, but the energy consumption of the process is increased, and when the temperature is less than the end point minimum of the range, the adverse effect is that an excessively low temperature can not chelate iron ions and other metal cations to form chelates, and the impurity removal in the third citric acid treatment solution is affected finally.
The second heating time is 15-20 min, and the positive effects are that in the time range, disodium ethylenediamine tetraacetate can be fully chelated with iron ions and other metal cations respectively to form chelate, so that agglomerates are fully formed, and solution is separated out; when the time value is larger than the end point maximum value of the range, the adverse effect is that the time consumption of the process is prolonged for too long, meanwhile, the energy consumption of the process is increased, and when the time value is smaller than the end point minimum value of the range, the adverse effect is that the chelate cannot be formed due to too short time, and further, the agglomerates cannot be fully formed, so that the third citric acid treatment solution without metal cations is not obtained.
The end temperature of the third heating is 110-118 ℃, and the positive effects are that in the temperature range, sodium salt and other substances which are formed by impurity acid and are sensitive to solubility can be separated out from the solution after the pH adjustment, and meanwhile, the pH is further adjusted, so that chelate in the solution can form agglomerates; when the temperature is greater than the end point maximum of the range, the adverse effect that would result is an excessively high temperature which, although accelerating the formation of the chelate in solution into agglomerates, would increase the solubility of the chelate, affect the amount of final agglomerates, cause incomplete removal of the metal cations, affect the removal of the final metal cations, and when the temperature is less than the end point minimum of the range, would result in an excessively low temperature which would not cause the chelate to form agglomerates.
The positive effect of the third heating time of 10 min-15 min is that in the time range, the chelate in the solution with the pH adjusted can be converted into the agglomerate in enough time, and meanwhile, sodium salt and other impurities sensitive to temperature can be separated out of the solution; when the time value is larger than the end point maximum value of the range, the adverse effect caused by the fact that the time is too long increases the time consumption of the process, meanwhile, the energy consumption of the process is increased, when the time value is smaller than the end point minimum value of the range, the adverse effect caused by the fact that the time is too short cannot convert the residual chelate into an aggregate, meanwhile, sodium salt and other impurities which are sensitive to temperature cannot be fully separated out of the solution, and the removing effect of impurities in the third sodium citrate solution is affected.
As an alternative embodiment, the first insulation includes: preserving heat for 20-25 min under the condition of the second temperature rising end point temperature;
the second insulation includes: and preserving heat for 15-20 min under the condition of the end temperature of the third heating.
In the application, the positive effect of the first heat preservation for 20-25 min is that disodium ethylenediamine tetraacetate can be fully chelated with iron ions and other metal cations respectively to form chelate in the time range, and then the chelate is converted into agglomerate; when the time is greater than the end point maximum value of the range, the adverse effect is that the too long time will cause the time consumption of the process to increase, and the energy consumption of the process to increase, which is unfavorable for environmental protection and energy saving, and when the time is less than the end point minimum value of the range, the adverse effect is that the chelating process cannot be sufficiently performed due to too short time, and the agglomeration cannot be sufficiently converted.
The second heat preservation for 15-20 min has the positive effects that in the time range, the chelate in the solution after pH adjustment can be converted into the agglomerate in enough time, and meanwhile, sodium salt and other impurities sensitive to temperature can be separated out of the solution; when the time is greater than the end point maximum of the range, the adverse effect caused by the excessively long time is that the time consumption of the process is increased, the energy consumption of the process is increased, the environment protection and the energy consumption saving are not facilitated, and when the time is smaller than the end point minimum of the range, the adverse effect caused by the excessively short time is that the chelate cannot be sufficiently converted into the agglomerate, and meanwhile, the sodium salt and other impurities which are sensitive to the temperature cannot be sufficiently separated into the solution.
As an alternative embodiment, the pH adjustment has an end point pH of 7.5 to 8.5.
In the present application, the positive effect of limiting the end point pH to 7.5 to 8.5 is that the pH of sodium citrate is higher than neutral pH because it is a weak acid, strong base salt.
As an alternative embodiment, the end temperature of the cooling is 50 ℃ to 65 ℃.
In the application, the positive effect that the final temperature of the cooling is 50-55 ℃ is that the solution is unstable in property after the pH is adjusted, so that unstable substances sensitive to the solubility can be separated out of the solution by cooling, and the solution is conveniently filtered out by the second fine filtration; when the temperature is higher than the end maximum of the range, an adverse effect is that an excessively high temperature will cause a part of the unstable substance sensitive to solubility to be difficult to be precipitated in the solution, and when the temperature is lower than the end minimum of the range, an excessively low temperature will cause a large amount of coolant to be required to precipitate the unstable substance sensitive to solubility, increasing the consumption of the process, while an excessively low temperature will cause a part of sodium citrate to be precipitated in the solution, resulting in a loss of solute.
As an alternative embodiment, both the first fine filtration and the second fine filtration comprise suction filtration under vacuum.
As an alternative embodiment, the decoloring includes: and (3) decoloring through activated carbon adsorption, wherein the mass volume ratio of the activated carbon to the fourth citric acid treatment solution is 2 g/mL-5 g/mL.
In the application, the active carbon and the fourth citric acid treatment solution have the positive effects that pigment molecules and other adsorbable impurities in the fourth citric acid treatment solution can be completely adsorbed within the mass-volume ratio range; when the value of the mass-to-volume ratio is larger than the end point maximum value of the range, the adverse effect caused by the fact that excessive activated carbon influences the cation adsorption process, and meanwhile, excessive activated carbon can shade, whether pigment molecules are completely adsorbed cannot be judged, and when the value of the mass-to-volume ratio is smaller than the end point minimum value of the range, the adverse effect caused by the fact that the value of the mass-to-volume ratio is smaller than the end point minimum value of the range is too small, pigment molecules cannot be fully absorbed, and the subsequent cation exchange resin adsorption process is influenced.
As an alternative embodiment, the diluted water consumption is 1.5 to 2.5 times the mass of the citric acid mother liquor;
the evaporation amount of the evaporation concentration accounts for 15-20% of the volume of the fourth citric acid treatment liquid.
In the application, the water consumption for dilution is limited to be 1.5-2.5 times of the mass of the citric acid mother solution, so that the dilution of the citric acid mother solution is strictly controlled, and the citric acid mother solution is prevented from being hydrolyzed due to excessive dilution, and the product quality of the sodium citrate is prevented from being influenced.
The positive effect that the evaporation amount of evaporation concentration accounts for 15-20% of the volume of the fourth citric acid treatment liquid is that in the range, part of impurities can be fully evaporated, and meanwhile, the other part of impurities can be separated out of the solution and can be removed through subsequent centrifugation; when the evaporation amount is larger than the end maximum value of the range, the adverse effect is that the excessive evaporation amount brings away part of sodium citrate solute, so that solute loss is caused, and when the evaporation amount is smaller than the end minimum value of the range, the adverse effect is that the excessive evaporation amount cannot evaporate impurities, so that pure sodium citrate solution is difficult to obtain.
Example 1
Referring to fig. 1, a method for purifying a citric acid mother solution, the method comprising:
s1, obtaining a citric acid mother solution;
s2, diluting the citric acid mother solution, and then adding an organic solvent for first heating to obtain a first citric acid treatment solution;
s3, adding disodium ethylenediamine tetraacetate into the first citric acid treatment solution, stirring and heating for the second time, and performing first heat preservation and first fine filtration to obtain a second citric acid treatment solution;
s4, adding the alkaline solution containing sodium into the second citric acid treatment solution, adjusting the pH value, and then carrying out third temperature rising and second heat preservation to obtain a third citric acid treatment solution;
s5, cooling the third citric acid treatment liquid, and performing second fine filtration to obtain a fourth citric acid treatment liquid;
s6, evaporating, concentrating and centrifuging the fourth citric acid treatment solution, and decoloring and treating with cation exchange resin to obtain a pure sodium citrate solution;
wherein the organic solvent is ethanol.
The mass ratio of the disodium ethylenediamine tetraacetate to the iron ions in the first citric acid treatment solution is 1.2.
The alkaline solution containing sodium is sodium hydroxide.
The end temperature of the first heating is 60 ℃, and the time of the first heating is 17min;
the end temperature of the second heating is 80 ℃, and the time of the second heating is 18min;
the final temperature of the third temperature rise is 115 ℃, and the time of the third temperature rise is 12min.
The first heat preservation includes: preserving heat for 23min under the condition of the second temperature rising end point temperature;
the second heat preservation includes: and (5) preserving heat for 17min under the condition of the end temperature of the third heating.
The end point pH of the pH adjustment was 8.
The final temperature of the cooling was 60 ℃.
Both the first fine filtration and the second fine filtration comprise suction filtration under vacuum.
The decoloring comprises the following steps: and (3) decoloring through activated carbon adsorption, wherein the mass-volume ratio of the activated carbon to the fourth citric acid treatment solution is 3g/mL.
The water consumption for dilution is 2 times of the mass of the citric acid mother solution;
the evaporation amount of the evaporation concentration accounts for 18% of the volume of the fourth citric acid treatment solution.
Example 2
Comparing example 2 with example 1, example 2 differs from example 1 in that:
the organic solvent is propanol.
The mass ratio of the disodium ethylenediamine tetraacetate to the iron ions in the first citric acid treatment solution was 0.8.
The alkaline solution containing sodium is sodium carbonate.
The end temperature of the first heating is 65 ℃, and the time of the first heating is 15min;
the end temperature of the second heating is 85 ℃, and the time of the second heating is 15min;
the final temperature of the third temperature rise is 118 ℃, and the time of the third temperature rise is 10min.
The first heat preservation includes: preserving heat for 20min under the condition of the second temperature rising end point temperature;
the second heat preservation includes: and (5) preserving heat for 15min under the condition of the end temperature of the third heating.
The final pH of the pH adjustment was 7.5.
The final temperature of the cooling was 50 ℃.
Both the first fine filtration and the second fine filtration comprise suction filtration under vacuum.
The decoloring comprises the following steps: and (3) decoloring through activated carbon adsorption, wherein the mass-volume ratio of the activated carbon to the fourth citric acid treatment solution is 2g/mL.
The water consumption for dilution is 1.5 times of the mass of the citric acid mother solution;
the evaporation amount of the evaporation concentration accounts for 15% of the volume of the fourth citric acid treatment solution.
Example 3
Comparing example 3 with example 1, example 3 differs from example 1 in that:
the organic solvent is methanol.
The mass ratio of the disodium ethylenediamine tetraacetate to the iron ions in the first citric acid treatment solution was 1.5.
The alkaline solution containing sodium is sodium bicarbonate.
The end temperature of the first heating is 50 ℃, and the time of the first heating is 20min;
the end temperature of the second heating is 75 ℃, and the time of the second heating is 20min;
the final temperature of the third temperature rise is 110 ℃, and the time of the third temperature rise is 15min.
The first heat preservation includes: preserving heat for 25min under the condition of the second temperature rising end point temperature;
the second heat preservation includes: and preserving heat for 20min under the condition of the end temperature of the third heating.
The final pH of the pH adjustment was 8.5.
The final temperature of the cooling was 65 ℃.
Both the first fine filtration and the second fine filtration comprise suction filtration under vacuum.
The decoloring comprises the following steps: and (3) decoloring through activated carbon adsorption, wherein the mass-volume ratio of the activated carbon to the fourth citric acid treatment solution is 5g/mL.
The water consumption for dilution is 2.5 times of the mass of the citric acid mother solution;
the evaporation amount of the evaporation concentration accounts for 20% of the volume of the fourth citric acid treatment solution.
Comparative example 1
Comparative example 1 and example 1 are compared, and the difference between comparative example 1 and example 1 is that:
and replacing disodium edetate with a sodium fermi solution, and simultaneously calculating the mass ratio of the corresponding sodium fermi solution to the iron ions.
Comparative example 2
Comparative example 2 and example 1 are compared, and the difference between comparative example 2 and example 1 is that:
the second temperature rise is performed directly by the third temperature rise condition without using the second temperature rise condition.
Comparative example 3
Comparative example 3 and example 1 are compared, and the difference between comparative example 3 and example 1 is that:
the end temperature of the first heating is 45 ℃, and the time of the first heating is 10min;
the end temperature of the second heating is 70 ℃, and the time of the second heating is 15min:
the final temperature of the third temperature rise is 105 ℃, and the time of the third temperature rise is 8min.
The first heat preservation includes: preserving heat for 15min under the condition of the second temperature rising end point temperature;
the second heat preservation includes: and preserving heat for 10min under the condition of the end temperature of the third heating.
Comparative example 4
Comparative example 4 and example 1 are compared, and the difference between comparative example 4 and example 1 is that:
the end temperature of the first heating is 70 ℃, and the time of the first heating is 25min;
the end temperature of the second heating is 90 ℃, and the time of the second heating is 25min;
the final temperature of the third temperature rise is 120 ℃, and the time of the third temperature rise is 20min.
The first heat preservation includes: preserving heat for 30min under the condition of the second temperature rising end point temperature;
the second heat preservation includes: and preserving heat for 25min under the condition of the end temperature of the third heating.
The sodium citrate solutions obtained in examples 1-3 and comparative examples 1-4 were collected and concentrated under the same concentration process and conditions, respectively, to obtain sodium citrate crystallized products, and the properties of the sodium citrate crystallized products of each example and comparative example were examined, and the results are shown in Table 1.
Test method of related experiment:
crystallinity of sodium citrate crystals: the measurement was carried out according to the standard of GB 1886.25-2016.
Metal ion content of sodium citrate: the measurement was carried out according to the standard of GB 1886.25-2016.
Content of easily charred sodium citrate: the measurement was carried out according to the standard of GB 1886.25-2016.
TABLE 1
The specific analysis of the sample in Table 1,
crystallinity refers to the proportion of sodium citrate crystal regions in sodium citrate crystallization, the higher the crystallinity, indicating that the higher the purity of sodium citrate.
The metal ion content refers to the metal ion content in sodium citrate crystals, and the lower the metal ion content, the lower the impurity metal ion content in sodium citrate.
The content of the easy charring substances refers to organic impurities which are easy to charre or easy to oxidize and color when meeting sulfuric acid in sodium citrate crystallization, and generally the residual protein, the lower the content of the easy charring substances, the lower the protein content in the sodium citrate crystallization.
From the data of examples 1-3, it can be seen that:
by adjusting the parameter conditions of the treatment process of the citric acid fermentation liquid, the crystallinity of citric acid crystals can be effectively controlled, and meanwhile, the quality of the obtained sodium citrate crystal product is excellent.
From the data of comparative examples 1-4, it can be seen that:
if sodium fermet is adopted to replace disodium ethylenediamine tetraacetate, although the sodium fermet has a certain effect, the sodium fermet is a toxic substance, and the low toxicity of disodium ethylenediamine tetraacetate is strong, so that the sodium fermet is not applicable to producing edible sodium citrate crystal products;
if the process parameter conditions are not adopted or are beyond the range of the process parameters, the influence on the crystallinity and the iron ion content of the citric acid crystallization product is larger.
One or more embodiments of the present application also have the following advantages or effects:
(1) According to the method provided by the embodiment of the application, the citric acid mother solution is chelated with the disodium ethylenediamine tetraacetate, and then is matched with various heating, heat preservation and pH adjustment processes, so that iron ions, proteins and other impurities sensitive to solubility in the citric acid mother solution can be sufficiently removed.
(2) The purity of the sodium citrate crystal finally obtained by the method provided by the embodiment of the application is more than or equal to 90 percent, the content of iron ions is less than or equal to 0.006 percent, and the content of easy carbide is less than or equal to 0.016 percent.
(3) According to the method provided by the embodiment of the application, the technological parameters can be integrated onto an automatic processing production line of the citric acid mother solution, so that the automatic processing of the citric acid mother solution is realized, and the production cost is further saved.
(4) The method provided by the embodiment of the application is basically harmless to human bodies because the reagents and the dosage used in the method are in a low-toxicity or nontoxic range, and can be applied to the production of food-grade sodium citrate products.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (4)

1. A method for purifying a citric acid mother liquor, the method comprising:
obtaining a citric acid mother solution;
diluting the citric acid mother solution, and then adding an organic solvent to perform first heating to obtain a first citric acid treatment solution; adding disodium ethylenediamine tetraacetate into the first citric acid treatment solution, stirring and heating for the second time, and performing first heat preservation and first fine filtration to obtain a second citric acid treatment solution;
adding an alkaline solution containing sodium into the second citric acid treatment solution, adjusting the pH value, and then carrying out third temperature rising and second heat preservation to obtain a third citric acid treatment solution;
cooling the third citric acid treatment liquid, and performing second fine filtration to obtain a fourth citric acid treatment liquid;
evaporating, concentrating and centrifuging the fourth citric acid treatment solution, and then decoloring and treating with cation exchange resin to obtain a pure sodium citrate solution;
the mass ratio of the disodium ethylenediamine tetraacetate to the iron ions in the first citric acid treatment solution is 0.8-1.5;
the alkaline solution containing sodium comprises at least one of sodium hydroxide, sodium carbonate and sodium bicarbonate;
the end temperature of the first heating is 50-65 ℃, and the time of the first heating is 15-20 min;
the end temperature of the second heating is 75-85 ℃, and the time of the second heating is 15-20 min;
the final temperature of the third heating is 110-118 ℃, and the time of the third heating is 10-15 min; the first insulation includes: preserving heat for 20-25 min under the condition of the second temperature rising end point temperature;
the second insulation includes: preserving heat for 15-20 min under the condition of the end temperature of the third heating;
the final pH of the pH adjustment is 7.5-8.5;
the final temperature of the cooling is 50-65 ℃.
2. The method of claim 1, wherein the first fine filtration and the second fine filtration each comprise suction filtration under vacuum.
3. The method of claim 1, wherein the decolorizing comprises: and (3) decoloring through activated carbon adsorption, wherein the mass volume ratio of the activated carbon to the fourth citric acid treatment solution is 2 g/mL-5 g/mL.
4. The method according to claim 1, wherein the diluted water consumption is 1.5-2.5 times the mass of the citric acid mother liquor;
the evaporation amount of the evaporation concentration accounts for 15-20% of the volume of the fourth citric acid treatment liquid.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106349057A (en) * 2016-08-29 2017-01-25 日照金禾博源生化有限公司 Treatment process for deferrization purification of sodium citrate mother liquor
CN106526011A (en) * 2016-11-03 2017-03-22 百奥森（江苏）食品安全科技有限公司 Detection method for heavy metal
CN108946857A (en) * 2018-07-24 2018-12-07 四川大航建设工程有限公司 Inorganic agent and processing method containing heavy metal containing sewage
CN110642707A (en) * 2019-10-22 2020-01-03 成都市科隆化学品有限公司 Purification production method of low-cost environment-friendly sodium salicylate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106349057A (en) * 2016-08-29 2017-01-25 日照金禾博源生化有限公司 Treatment process for deferrization purification of sodium citrate mother liquor
CN106526011A (en) * 2016-11-03 2017-03-22 百奥森（江苏）食品安全科技有限公司 Detection method for heavy metal
CN108946857A (en) * 2018-07-24 2018-12-07 四川大航建设工程有限公司 Inorganic agent and processing method containing heavy metal containing sewage
CN110642707A (en) * 2019-10-22 2020-01-03 成都市科隆化学品有限公司 Purification production method of low-cost environment-friendly sodium salicylate

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