CN112457185A - Iron-removing purification process for potassium citrate mother liquor - Google Patents

Iron-removing purification process for potassium citrate mother liquor Download PDF

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Publication number
CN112457185A
CN112457185A CN201910849714.2A CN201910849714A CN112457185A CN 112457185 A CN112457185 A CN 112457185A CN 201910849714 A CN201910849714 A CN 201910849714A CN 112457185 A CN112457185 A CN 112457185A
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solution
potassium citrate
mother liquor
citrate mother
purification process
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Inventor
李明达
潘学成
彭莱
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Lianyungang Shuren Kechuang Food Additive Co ltd
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Lianyungang Shuren Kechuang Food Additive Co ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42Separation; Purification; Stabilisation; Use of additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A potassium citrate mother liquor deferrization purification process comprises the following specific steps: (1) adding pure water into the last potassium citrate mother liquor to dilute the potassium citrate mother liquor, and then heating the solution to 60-80 ℃ to obtain a solution A; (2) adding citric acid into the solution A, and adjusting the pH value to 6.5-8.0 to obtain a solution B; (3) adding a certain amount of hydrogen peroxide into the solution B to oxidize ferrous iron in the solution B into ferric iron to obtain solution C; (4) enabling the solution C to pass through an ion exchange column filled with cation resin according to the flow rate of 150L/h-200L/h to obtain a solution D; (5) enabling the solution D to pass through an activated carbon column according to the flow rate of 150L/h-200L/h, and removing the carbon-prone compound to obtain a solution E; (6) and evaporating, crystallizing, centrifugally separating and drying the solution E to obtain a potassium citrate product. The process for purifying the potassium citrate mother liquor can effectively remove iron and easily-carbonized compounds in the potassium citrate mother liquor, improve the yield of the potassium citrate by about 5 percent, realize zero emission of the potassium citrate mother liquor and have remarkable economic benefit and environmental protection benefit.

Description

Iron-removing purification process for potassium citrate mother liquor
Technical Field
The invention relates to the technical field of food additives, in particular to a process for removing iron and purifying potassium citrate mother liquor.
Background
The potassium citrate is colorless crystal or white crystalline powder, is easily soluble in water, and tastes salty and cool. In the food industry, buffers, chelating agents, stabilizers, antioxidants, emulsifiers and the like can be used, and in the pharmaceutical industry, the buffers, chelating agents, stabilizers, antioxidants, emulsifiers and the like can be used as anticoagulants, hypokalemia and alkalinized urine treatments.
The production process of potassium citrate is to dissolve citric acid in water and potassium hydroxide solution to carry out neutralization reaction to generate potassium citrate solution. And (3) carrying out fine filtration, evaporative crystallization, centrifugal separation and drying on the potassium citrate solution obtained by the reaction to obtain a finished product of the potassium citrate.
In the industrial production process of potassium citrate, a large amount of final potassium citrate mother liquor is generated, and the mother liquor contains high metal ions such as iron and the like, a small amount of protein colloid, organic impurities and other substances which are easy to carbonize, so that the color of the potassium citrate mother liquor is darkened, the viscosity of the potassium citrate mother liquor is increased, qualified potassium citrate finished products cannot be crystallized, and the potassium citrate finished products can only be used as waste liquor to enter a sewage treatment system. This not only causes huge waste of resources and reduces the yield of potassium citrate product, but also invests in special sewage treatment equipment and costs a lot of treatment cost. The main factors influencing the quality of the potassium citrate through research are iron and easy-to-carbonize compounds in the mother solution, when the content of iron ions in the potassium citrate is more than 10ppm, the product turns yellow, the light transmittance is obviously reduced, and the product quality is obviously reduced. Therefore, if the existing potassium citrate final mother liquor can be purified, the content of iron in the potassium citrate mother liquor is reduced, the standard potassium citrate is obtained, and the yield of the potassium citrate in the production of the potassium citrate can be obviously improved.
Disclosure of Invention
The invention aims to make up for the defects of the prior art and provides a method which is simple in process and can effectively remove iron ions in a potassium citrate mother solution and easily combine with charcoal, so that the quality of prepared potassium citrate is improved.
In order to achieve the purpose, the invention is realized by the following scheme:
the invention provides a potassium citrate mother liquor iron removal purification process, which comprises the following specific steps:
(1) adding pure water into the last potassium citrate mother liquor to dilute the potassium citrate mother liquor, and then heating the solution to 60-80 ℃ to obtain a solution A;
(2) adding citric acid into the solution A obtained in the step (1), and adjusting the pH value to 6.5-8.0 to obtain a solution B;
(3) adding a certain amount of hydrogen peroxide into the solution B obtained in the step (2), and oxidizing ferrous iron in the solution B into ferric iron to obtain a solution C;
(4) enabling the solution C obtained in the step (3) to pass through an ion exchange column filled with cation resin according to the flow rate of 150L/h-200L/h to obtain a solution D, resolving iron ions by using dilute hydrochloric acid after the resin is saturated, and regenerating by using a dilute potassium hydroxide solution;
(5) enabling the solution D obtained in the step (4) to pass through an activated carbon column according to the flow rate of 150L/h-200L/h, and removing carbon-prone compounds to obtain a solution E;
(6) and (5) evaporating, crystallizing, centrifuging and drying the solution E obtained in the step (5) to obtain a potassium citrate product.
Preferably, the diluted specific gravity of the final potassium citrate mother liquor in the step (1) is 1.30-1.35.
Preferably, the cationic resin is one of chelating resins.
Preferably, solution B has a pH of 6.5 to 7.5.
Preferably, the volume of the hydrogen peroxide added in the step (3) is 0.1 percent of the volume of the solution B.
Preferably, the iron content of the solution D in the step (4) is controlled to be 0.5-1.0ppm, and the concentration of hydrochloric acid and potassium hydroxide used is 4-8%.
Preferably, the activated carbon is granular activated carbon.
Preferably, the ion exchange column in step (4) is used in series with the activated carbon column in step (5).
Preferably, the light transmittance of solution E is greater than or equal to 90%.
The invention has the beneficial effects that:
according to the potassium citrate mother liquor purification process, after dilution and pH adjustment, ferrous iron in the potassium citrate mother liquor is oxidized into ferric iron by using hydrogen peroxide, iron ions in the mother liquor are removed through an ion exchange membrane, easily-carbonized compounds in the potassium citrate mother liquor are removed through activated carbon, finally the purified mother liquor is subjected to evaporative crystallization, centrifugal separation and drying to obtain a potassium citrate product, the iron content in the potassium citrate product is stabilized within 5ppm, the light transmittance is stabilized above 95%, the potassium citrate yield is improved by about 5%, zero emission of the potassium citrate mother liquor is achieved, and economic benefits and environmental protection benefits are remarkable.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A potassium citrate mother liquor deferrization purification process comprises the following specific steps:
(1) adding pure water into the last potassium citrate mother liquor, diluting the pure water to the specific gravity of 1.30, and heating the pure water to 60 ℃ under stirring to obtain a solution A;
(2) adding citric acid into the solution A obtained in the step (1), and adjusting the pH value to 6.5 to obtain a solution B;
(3) adding hydrogen peroxide with the volume of 0.1 percent of that of the solution B obtained in the step (2) into the solution B to obtain solution C;
(4) enabling the solution C obtained in the step (3) to pass through an ion exchange column filled with cation resin according to the flow rate of 150L/h to obtain a solution D;
(5) enabling the solution D obtained in the step (4) to pass through an activated carbon column according to the flow rate of 150L/h, and removing the compounds easy to carbonize by utilizing the adsorption decoloration effect of activated carbon to obtain a solution E;
(6) and (5) evaporating, crystallizing, centrifuging and drying the solution E obtained in the step (5) to obtain a potassium citrate product.
Through detection, the content of potassium citrate is as follows: 99.7%, iron salt content: 4.1ppm, transmittance: 97 percent; easy carbonization: less than or equal to 1 percent. The product quality completely meets the requirements of GB 1886.74-2015.
Example 2
A potassium citrate mother liquor deferrization purification process comprises the following specific steps:
(1) adding pure water into the last potassium citrate mother liquor, diluting the pure water to the specific gravity of 1.32, and heating the pure water to 70 ℃ under stirring to obtain a solution A;
(2) adding citric acid into the solution A obtained in the step (1), and adjusting the pH value to 7.0 to obtain a solution B;
(3) adding hydrogen peroxide with the volume of 0.1 percent of that of the solution B obtained in the step (2) into the solution B to obtain solution C;
(4) enabling the solution C obtained in the step (3) to pass through an ion exchange column filled with cation resin according to the flow rate of 180L/h to obtain a solution D;
(5) enabling the solution D obtained in the step (4) to pass through an activated carbon column according to the flow of 180L/h, and removing the compounds easy to carbonize by utilizing the adsorption decoloration effect of activated carbon to obtain a solution E;
(6) and (5) evaporating, crystallizing, centrifuging and drying the solution E obtained in the step (5) to obtain a potassium citrate product.
Through detection, the content of potassium citrate is as follows: 99.6%, iron salt content: 4.3ppm, transmittance: 96.5 percent; easy carbonization: less than or equal to 1 percent. The product quality completely meets the requirements of GB 1886.74-2015.
Example 3
A potassium citrate mother liquor deferrization purification process comprises the following specific steps:
(1) adding pure water into the last potassium citrate mother liquor, diluting the pure water to the specific gravity of 1.35, and heating the pure water to 70 ℃ under stirring to obtain a solution A;
(2) adding citric acid into the solution A obtained in the step (1), and adjusting the pH value to 7.5 to obtain a solution B;
(3) adding hydrogen peroxide with the volume of 0.1 percent of that of the solution B obtained in the step (2) into the solution B to obtain solution C;
(4) enabling the solution C obtained in the step (3) to pass through an ion exchange column filled with cation resin according to the flow rate of 180L/h to obtain a solution D;
(5) enabling the solution D obtained in the step (4) to pass through an activated carbon column according to the flow of 180L/h, and removing the compounds easy to carbonize by utilizing the adsorption decoloration effect of activated carbon to obtain a solution E;
(6) and (5) evaporating, crystallizing, centrifuging and drying the solution E obtained in the step (5) to obtain a potassium citrate product.
Through detection, the content of potassium citrate is as follows: 99.5%, iron salt content: 4.4ppm, transmittance: 95.8 percent; easy carbonization: less than or equal to 1 percent. The product quality completely meets the requirements of GB 1886.74-2015.
Example 4
A potassium citrate mother liquor deferrization purification process comprises the following specific steps:
(1) adding pure water into the last potassium citrate mother liquor, diluting the pure water to the specific gravity of 1.35, and heating the pure water to 80 ℃ under stirring to obtain a solution A;
(2) adding citric acid into the solution A obtained in the step (1), and adjusting the pH value to 8.0 to obtain a solution B;
(3) adding hydrogen peroxide with the volume of 0.1 percent of that of the solution B obtained in the step (2) into the solution B to obtain solution C;
(4) enabling the solution C obtained in the step (3) to pass through an ion exchange column filled with cation resin according to the flow rate of 200L/h to obtain a solution D;
(5) enabling the solution D obtained in the step (4) to pass through an activated carbon column according to the flow of 200L/h, and removing the compounds easy to carbonize by utilizing the adsorption decoloration effect of activated carbon to obtain a solution E;
(6) and (5) evaporating, crystallizing, centrifuging and drying the solution E obtained in the step (5) to obtain a potassium citrate product.
Through detection, the content of potassium citrate is as follows: 99.5%, iron salt content: 4.5ppm, transmittance: 96 percent; easy carbonization: less than or equal to 1 percent. The product quality completely meets the requirements of GB 1886.74-2015.
Example 5
A potassium citrate mother liquor deferrization purification process comprises the following specific steps:
(1) adding pure water into the last potassium citrate mother liquor, diluting the pure water to the specific gravity of 1.30, and heating the pure water to 65 ℃ under stirring to obtain a solution A;
(2) adding citric acid into the solution A obtained in the step (1), and adjusting the pH value to 7.0 to obtain a solution B;
(3) adding hydrogen peroxide with the volume of 0.1 percent of that of the solution B obtained in the step (2) into the solution B to obtain solution C;
(4) enabling the solution C obtained in the step (3) to pass through an ion exchange column filled with cation resin according to the flow rate of 150L/h to obtain a solution D;
(5) enabling the solution D obtained in the step (4) to pass through an activated carbon column according to the flow rate of 150L/h, and removing the compounds easy to carbonize by utilizing the adsorption decoloration effect of activated carbon to obtain a solution E;
(6) and (5) evaporating, crystallizing, centrifuging and drying the solution E obtained in the step (5) to obtain a potassium citrate product.
Through detection, the content of potassium citrate is as follows: 99.7%, iron salt content: 4.2ppm, transmittance: 96.2 percent; easy carbonization: less than or equal to 1 percent. The product quality completely meets the requirements of GB 1886.74-2015.
Example 6
A potassium citrate mother liquor deferrization purification process comprises the following specific steps:
(1) adding pure water into the last potassium citrate mother liquor, diluting the pure water to the specific gravity of 1.35, and heating the pure water to 75 ℃ under stirring to obtain a solution A;
(2) adding citric acid into the solution A obtained in the step (1), and adjusting the pH value to 7.5 to obtain a solution B;
(3) adding hydrogen peroxide with the volume of 0.1 percent of that of the solution B obtained in the step (2) into the solution B to obtain solution C;
(4) enabling the solution C obtained in the step (3) to pass through an ion exchange column filled with cation resin according to the flow rate of 160L/h to obtain a solution D;
(5) enabling the solution D obtained in the step (4) to pass through an activated carbon column according to the flow of 160L/h, and removing the compounds easy to carbonize by utilizing the adsorption and decoloration effects of activated carbon to obtain a solution E;
(6) and (5) evaporating, crystallizing, centrifuging and drying the solution E obtained in the step (5) to obtain a potassium citrate product.
Through detection, the content of potassium citrate is as follows: 99.6%, iron salt content: 4.1ppm, transmittance: 96.5 percent; easy carbonization: less than or equal to 1 percent. The product quality completely meets the requirements of GB 1886.74-2015.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not exhaustive or limiting of the specific embodiments of the invention. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (9)

1. A potassium citrate mother liquor deferrization purification process is characterized by comprising the following specific steps:
(1) adding pure water into the last potassium citrate mother liquor to dilute the potassium citrate mother liquor, and then heating the solution to 60-80 ℃ to obtain a solution A;
(2) adding citric acid into the solution A obtained in the step (1), and adjusting the pH value to 6.5-8.0 to obtain a solution B;
(3) adding a certain amount of hydrogen peroxide into the solution B obtained in the step (2), and oxidizing ferrous iron in the solution B into ferric iron to obtain a solution C;
(4) enabling the solution C obtained in the step (3) to pass through an ion exchange column filled with cation resin according to the flow rate of 150L/h-200L/h to obtain a solution D, resolving iron ions by using dilute hydrochloric acid after the resin is saturated, and regenerating by using a dilute potassium hydroxide solution;
(5) enabling the solution D obtained in the step (4) to pass through an activated carbon column according to the flow rate of 150L/h-200L/h, and removing carbon-prone compounds to obtain a solution E;
(6) and (5) evaporating, crystallizing, centrifuging and drying the solution E obtained in the step (5) to obtain a potassium citrate product.
2. The potassium citrate mother liquor deferrization purification process according to claim 1, characterized in that the final potassium citrate mother liquor in the step (1) has a dilution specific gravity of 1.30-1.35.
3. The potassium citrate mother liquor deferrization purification process according to claim 1, characterized in that the cationic resin is one of chelating resins.
4. The potassium citrate mother liquor deferrization purification process according to claim 1, characterized in that the pH of the solution B is 6.5-7.5.
5. The potassium citrate mother liquor deferrization purification process of claim 1, wherein the volume of hydrogen peroxide added in the step (3) is 0.1% of the volume of the solution B.
6. The potassium citrate mother liquor deferrization purification process according to claim 1, characterized in that in the step (4), the iron content in the solution D is controlled to be 0.5-1.0ppm, and the concentration of the hydrochloric acid and the potassium hydroxide is controlled to be 4-8%.
7. The potassium citrate mother liquor deferrization and purification process of claim 1, wherein the activated carbon is granular activated carbon.
8. The potassium citrate mother liquor deferrization and purification process of claim 1, wherein the ion exchange column in the step (4) is connected with the activated carbon column in the step (5) in series for use.
9. The potassium citrate mother liquor deferrization purification process according to claim 1, characterized in that the light transmittance of the solution E is not less than 90%.
CN201910849714.2A 2019-09-09 2019-09-09 Iron-removing purification process for potassium citrate mother liquor Pending CN112457185A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113372213A (en) * 2021-05-18 2021-09-10 连云港陆兴科技有限公司 Production system and method of potassium citrate
CN114315502A (en) * 2021-12-31 2022-04-12 南京化学试剂股份有限公司 Method for purifying low-moisture high-purity xylene

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GB905817A (en) * 1960-02-01 1962-09-12 Miles Lab Improvements in the purification of citric acid
CN1083470A (en) * 1993-06-10 1994-03-09 李秀 The method of producing citric acit from acetylene offscum
DE19747902A1 (en) * 1997-10-30 1999-05-12 Metallgesellschaft Ag Process for the production of citric acid and / or citrates
WO2007051309A1 (en) * 2005-11-04 2007-05-10 Alternate Energy Corporation Process for preparing a metallic salt and recovering hydrogen gas
CN101407454A (en) * 2007-10-13 2009-04-15 黄石兴华生化有限公司 Process for preparing citrate salt from mother liquor for citric acid production
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CN103864604A (en) * 2014-02-25 2014-06-18 日照金禾博源生化有限公司 Purification treatment technology for iron removal from sodium citrate mother liquor
CN103896762A (en) * 2012-12-28 2014-07-02 中粮营养健康研究院有限公司 Purifying method of citric acid-containing solution
CN104045551A (en) * 2014-05-27 2014-09-17 日照金禾博源生化有限公司 Recycling method of unqualified sodium citrate mother liquor
CN105061196A (en) * 2015-09-15 2015-11-18 安徽丰原发酵技术工程研究有限公司 Method for extracting potassium citrate from last potassium citrate mother solution

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2883329A (en) * 1955-07-11 1959-04-21 Melle Usines Sa Process for producing citric acid
GB905817A (en) * 1960-02-01 1962-09-12 Miles Lab Improvements in the purification of citric acid
CN1083470A (en) * 1993-06-10 1994-03-09 李秀 The method of producing citric acit from acetylene offscum
DE19747902A1 (en) * 1997-10-30 1999-05-12 Metallgesellschaft Ag Process for the production of citric acid and / or citrates
WO2007051309A1 (en) * 2005-11-04 2007-05-10 Alternate Energy Corporation Process for preparing a metallic salt and recovering hydrogen gas
CN101407454A (en) * 2007-10-13 2009-04-15 黄石兴华生化有限公司 Process for preparing citrate salt from mother liquor for citric acid production
WO2012154498A2 (en) * 2011-05-06 2012-11-15 Advanced Technology Materials, Inc. Removal of metal impurities from silicon surfaces for solar cell and semiconductor applications
CN103896762A (en) * 2012-12-28 2014-07-02 中粮营养健康研究院有限公司 Purifying method of citric acid-containing solution
CN103864604A (en) * 2014-02-25 2014-06-18 日照金禾博源生化有限公司 Purification treatment technology for iron removal from sodium citrate mother liquor
CN104045551A (en) * 2014-05-27 2014-09-17 日照金禾博源生化有限公司 Recycling method of unqualified sodium citrate mother liquor
CN105061196A (en) * 2015-09-15 2015-11-18 安徽丰原发酵技术工程研究有限公司 Method for extracting potassium citrate from last potassium citrate mother solution

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113372213A (en) * 2021-05-18 2021-09-10 连云港陆兴科技有限公司 Production system and method of potassium citrate
CN114315502A (en) * 2021-12-31 2022-04-12 南京化学试剂股份有限公司 Method for purifying low-moisture high-purity xylene

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