CN115784980A - Method for recovering and treating chromium picolinate mother liquor - Google Patents

Abstract

The invention discloses a method for recovering and treating chromium picolinate mother liquor. The method comprises the following steps: adding the carrier into a stirring kettle containing chromium picolinate mother liquor, and stirring uniformly by starting stirring; adding an anticaking agent into the solution, and continuously stirring uniformly; adding a surfactant into the solution, and continuously stirring uniformly; and (4) placing the treated solution in a spray drying tower for spray drying to obtain a chromium picolinate premixed small material product. The process is safe and reliable, has strong operability, and can fully recover the chromium picolinate in the chromium picolinate mother liquor for recycling.

Description

A kind of recovery processing method of chromium picolinate mother liquor

technical field

The invention relates to a recovery treatment method, in particular to a recovery treatment method for chromium picolinate mother liquor.

Background technique

Chromium picolinate is a functional ingredient that is allowed by the Ministry of Health and can be added to health food. It is recognized as an ideal chromium source supplement and is mainly used in medicine, health food and feed additives. Adding some organic chromium in food can reduce the blood sugar level and insulin resistance of diabetic patients, prevent and treat diabetes, and as a feed additive for livestock and poultry, it is beneficial to the growth and development of animals.

Chromium picolinate, also known as chromium picolinate, chromium picolinate, chromium pyridine formate, is a complex of 2-picolinic acid and Cr compound, the molecular formula is Cr(CHNO), the molecular weight is 418.33, and it is purple-red Crystalline fine powder, good fluidity, stable at room temperature, slightly soluble in water, insoluble in ethanol, belonging to fat-soluble non-electrolyte, can pass through the cell membrane and directly act on the tissue.

At present, there are many ways to synthesize chromium 2-picolinate, which mainly include the following forms: 2-cyanopyridine is used as the main raw material, and 2-picolinic acid or sodium picolinate is synthesized by acid or alkali hydrolysis and other raw materials The synthesized 2-picolinic acid or sodium picolinate is chelated with trivalent chromium salt directly or indirectly through alkaline solution titration to generate chromium 2-picolinate. The color of chromium picolinate synthesized by this type of process is not uniform, and it is not suitable to control the intermediate pH value. The product The yield is also unstable, which is unfavorable for industrialized standard operation.

Put 2-cyanopyridine, one or more of sulfuric acid, hydrochloric acid or nitric acid, and trivalent chromium salt in a high-pressure reactor to synthesize chromium 2-picolinate. This type of process requires high production equipment and is a pressure There are certain safety hazards in the production process of containers. Decompose 2-picoline or 2-vinylpyridine with potassium permanganate, remove manganese dioxide and synthesize chromium 2-picolinate with trivalent chromium salt. In this type of process, potassium permanganate is expensive and produces a large amount of The by-product manganese dioxide has certain environmental risks.

The above chromium picolinate process technology does not propose how to recycle the chromium picolinate mother liquor, and there is an environmental protection problem, which leads to high production cost of chromium picolinate. In the industry, some enterprises need to settle the chromium picolinate mother liquor for a long time, and dry and pulverize the solid chromium picolinate recovered after the precipitation together with the chromium picolinate recovered by evaporating the separated mother liquor . The process for recovering chromium picolinate has high energy consumption and long time consumption, and the product is easy to agglomerate because it contains sodium chloride.

Contents of the invention

Aiming at the deficiencies of the existing technology, the present invention provides a chromium picolinate mother liquor with simple recovery route, safe and reliable technological process and strong operability, capable of fully recovering the chromium picolinate in the chromium picolinate mother liquor and recycling it for use.

The technical scheme of the present invention is as follows.

A kind of recovery processing method of chromium picolinate mother liquor, comprises the steps:

(1) The carrier is added to the stirred tank containing the chromium picolinate mother liquor, and the stirring is started to stir evenly to obtain the solution A;

(2) Add an anticaking agent to the solution A obtained in step (1), and continue to stir evenly to obtain a solution B;

(3) Add a surfactant to the solution B obtained in step (2), and continue to stir evenly to obtain a solution C;

(4) The solution C obtained in step (3) is sent to a spray drying tower for spray drying to obtain a chromium picolinate premixed small product.

In the above method, in step (1), the carrier is at least one of silica micropowder, light calcium carbonate, water-soluble starch, water-soluble maltodextrin and corncob powder.

In the above method, in step (1), the mass ratio of chromium picolinate to the carrier in the mother liquor containing chromium picolinate is 1:0.1-1000.

In the above method, in step (2), the anti-caking agent is one or more of calcium phosphate, microcrystalline cellulose, magnesium stearate, alkyl glycoside 0810 and ferric ammonium citrate.

In the above method, in step (2), the amount of anti-caking agent added satisfies: the mass ratio of chromium picolinate to anti-caking agent in the mother liquor containing chromium picolinate is 1:0.01-2.

In the above method, in step (3), the surface activity is more than one of sodium dodecylsulfonate, alkylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether;

The addition amount of the surfactant satisfies that the mass ratio of the chromium picolinate to the surfactant in the chromium picolinate-containing mother liquor is 1:0.0001-0.001.

In the above method, in step (4), the air temperature at the inlet of the spray drying tower is 150-350°C, and the air temperature at the outlet is 100-200°C. Preferably, the air temperature at the inlet of the spray drying tower is 300°C, and the air temperature at the outlet is 120°C.

In the above method, in step (3), after adding the surfactant and stirring evenly, then adding gelatin, then raising the temperature of the solution to 50° C., maintaining it for 1-2 hours, and then cooling down to normal temperature.

In the above method, the addition amount of the gelatin satisfies that the mass ratio of chromium picolinate to gelatin is 1:0.01-2.

Compared with the prior art, the present invention has the advantages of:

The present invention is different from the prior art. The technological process of the present invention is safe and reliable, and has strong operability, and can fully recover the chromium picolinate in the chromium picolinate mother liquor, and recycle and use it.

The invention effectively solves the problems of high production cost, non-environmental protection and large equipment loss in the synthesis of picolinic acid products, reduces production cost and improves economic benefits.

The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

Description of drawings

Fig. 1 is the product picture in embodiment 1;

Fig. 2 is the product picture of embodiment 2;

Fig. 3 is the product picture of comparative example 1.

Detailed ways

Below in conjunction with accompanying drawing and specific embodiment the present invention is described in further detail:

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

Example 1

(1) Add water-soluble starch into a stirred tank containing chromium picolinate mother liquor (1kg), stir well, wherein the mass ratio of chromium picolinate and water-soluble starch is 1:1. Before this step, it is necessary to analyze the chromium picolinate in the mother liquor. In this embodiment, the content of chromium picolinate in the mother liquor is analyzed to be 2.70% by mass, and the mass percentage of solids is 10.01%.

(2) Add calcium phosphate anti-caking agent to the stirred tank solution, the mass ratio of chromium picolinate and calcium phosphate anti-caking agent is 1:1, and continue to stir evenly.

(3) Add sodium dodecylsulfonate surfactant into the stirred tank solution, the mass ratio of chromium picolinate and sodium dodecylsulfonate surfactant is 1:0.001, and continue to stir evenly.

(4) Send the stirred tank solution after mixing to the spray drying tower with an inlet air temperature of 300°C and an outlet air temperature of 120°C for spray drying to obtain the chromium picolinate premix product, which contains 17.52% chromium picolinate .

This embodiment is an optimal embodiment of the present application. From this embodiment, through the control of the reaction conditions and the control of the type of reaction raw materials, the optimal effect is achieved. Water-soluble starch, calcium phosphate anticaking agent and The addition of sodium dodecylsulfonate surfactant makes the recovery and treatment of chromium picolinate mother liquor perfect, and the final effect achieves the ideal effect whether it is color difference or agglomeration degree.

Example 2

(1) Add water-soluble maltodextrin into the stirred tank containing chromium picolinate mother liquor (1kg), start stirring and stir well, the mass ratio of chromium picolinate and water-soluble maltodextrin added is 1:10. Before this step, it is necessary to analyze the chromium picolinate in the mother liquor. In this embodiment, the content of chromium picolinate in the mother liquor is analyzed to be 2.70% by mass, and the mass percentage of solids is 10.01%.

(2) Add microcrystalline cellulose anti-caking agent to the stirred tank solution, the mass ratio of chromium picolinate and microcrystalline cellulose anti-caking agent is 1:0.5, and continue to stir evenly.

(3) Add alkylphenol polyoxyethylene ether surfactant to the stirred tank solution, the mass ratio of chromium picolinate and alkylphenol polyoxyethylene ether surfactant is 1:0.002, and continue to stir evenly.

(4) Send the stirred tank solution after mixing to an inlet air temperature of 350° C. and an outlet air temperature of 130° C. in a spray drying tower for spray drying to obtain a chromium picolinate premix product, which contains 7.04% chromium picolinate .

Example 3

(1) Add corn cob powder to a stirred tank containing chromium picolinate mother liquor (1kg), start stirring and stir well, the mass ratio of chromium picolinate and corn cob powder added is 1:20. Before this step, it is necessary to analyze the chromium picolinate in the mother liquor. In this embodiment, the content of chromium picolinate in the mother liquor is analyzed to be 2.70% by mass, and the mass percentage of solids is 10.01%.

(2) Add magnesium stearate anti-caking agent to the stirred tank solution, the mass ratio of chromium picolinate and magnesium stearate anti-caking agent is 1:0.8, and continue to stir evenly.

(3) Add fatty alcohol polyoxyethylene ether surfactant to the stirred tank solution, the mass ratio of chromium picolinate to fatty alcohol polyoxyethylene ether surfactant is 1:0.003, and continue to stir evenly.

(4) Send the stirred tank solution after mixing to the spray drying tower with an inlet air temperature of 280°C and an outlet air temperature of 115°C for spray drying to obtain a chromium picolinate premix product, which contains 4.08% chromium picolinate .

Example 4

(1) Add silicon dioxide micropowder into a stirred tank containing chromium picolinate mother liquor (1kg), start stirring and stir evenly, wherein the mass ratio of chromium picolinate and silicon dioxide micropowder added is 1:30. Before this step, it is necessary to analyze the chromium picolinate in the mother liquor. In this embodiment, the content of chromium picolinate in the mother liquor is analyzed to be 2.70% by mass, and the mass percentage of solids is 10.01%.

(2) Add ferric ammonium citrate anti-caking agent to the stirred tank solution, the mass ratio of chromium picolinate and ferric ammonium citrate anti-caking agent is 1:1.2, and continue to stir evenly.

(3) Add sodium dodecylsulfonate surfactant into the stirred tank solution, the mass ratio of chromium picolinate and sodium dodecylsulfonate surfactant is 1:0.001, and continue to stir evenly.

(4) Send the stirred tank solution after mixing to the spray drying tower with an inlet air temperature of 300°C and an outlet air temperature of 120°C for spray drying to obtain a chromium picolinate premix product, and the premix small material contains 2.86% chromium picolinate .

Example 5

(1) Add silicon dioxide micropowder and water-soluble starch into a stirred tank containing chromium picolinate mother liquor (1kg), start stirring and stir evenly, wherein the mass of chromium picolinate, silicon dioxide micropowder and water-soluble starch The ratio is 1:30, and the mass ratio of silica micropowder to water-soluble starch is 1:1. Before this step, the chromium picolinate in the mother liquor needs to be analyzed. In the present embodiment, the content quality of the chromium picolinate in the mother liquor analyzed is 2.70%, and the solid matter percentage is 10.01%.

(2) add calcium phosphate and magnesium stearate anti-caking agent in stirred tank solution, the mass ratio of chromium picolinate and anti-caking agent addition is 1: 1.2, continue to stir; Described calcium phosphate and magnesium stearate The mass ratio is 1:1.2.

(3) Add sodium dodecylsulfonate surfactant into the stirred tank solution, the mass ratio of chromium picolinate and sodium dodecylsulfonate surfactant is 1:0.001, and continue to stir evenly.

(4) Send the stirred tank solution after mixing to the spray drying tower with an inlet air temperature of 300°C and an outlet air temperature of 120°C for spray drying to obtain a chromium picolinate premix product, and the premix small material contains 2.86% chromium picolinate .

Example 6

(1) Add silicon dioxide micropowder and water-soluble starch to the stirred tank containing chromium picolinate mother liquor (1kg), start stirring and stir evenly, the addition amount of chromium picolinate and water-soluble starch in silicon dioxide micropowder and the The mass ratio is 1:20, and the mass ratio of silica micropowder to water-soluble starch is 1:1.5. Before this step, the chromium picolinate in the mother liquor needs to be analyzed. In the present embodiment, the content quality of the chromium picolinate in the mother liquor analyzed is 2.70%, and the solid matter percentage is 10.01%.

(2) Add alkyl glucoside 0810 and ferric ammonium citrate anti-caking agent in the stirred tank solution, the mass ratio of chromium picolinate and anti-caking agent added is 1:2, continue to stir evenly; described alkyl glucoside 0810 and The mass ratio of ferric ammonium citrate is 1:1.

(3) Add sodium dodecylsulfonate surfactant into the stirred tank solution, the mass ratio of chromium picolinate and sodium dodecylsulfonate surfactant is 1:0.001, and continue to stir evenly.

(4) Send the stirred tank solution after mixing to the spray drying tower with an inlet air temperature of 300°C and an outlet air temperature of 120°C for spray drying to obtain a chromium picolinate premix product, which contains 3.89% chromium picolinate .

Example 7

(1) Add the water-soluble starch into the stirring tank containing the chromium picolinate mother liquor (1kg), start stirring and stir well, wherein the mass ratio of the chromium picolinate and the water-soluble starch added is 1:30. Before this step, it is necessary to analyze the chromium picolinate in the mother liquor. In this embodiment, the content of chromium picolinate in the mother liquor is analyzed to be 2.70% by mass, and the mass percentage of solids is 10.01%.

(2) Add calcium phosphate anti-caking agent to the stirred tank solution, the mass ratio of chromium picolinate and calcium phosphate anti-caking agent is 1:1, and continue to stir evenly.

(3) Add sodium dodecylsulfonate surfactant in the stirred tank solution, the mass ratio of chromium picolinate and sodium dodecylsulfonate surfactant is 1:0.001, continue to stir evenly, then add gelatin, After the temperature of the solution was raised to 50° C., the solution was stirred and maintained for 2 hours. The mass ratio of chromium picolinate to gelatin was 1:0.2.

(4) Send the stirred tank solution after mixing to the spray drying tower with an inlet air temperature of 300°C and an outlet air temperature of 120°C for spray drying to obtain a chromium picolinate premix product, and the premix small material contains 2.86% chromium picolinate .

In this embodiment, the gelatin is added and treated at the same time by raising the temperature. The gelatin can wrap the effective substances in the treated mother liquor in the gelatin structure. Since the gelatin structure is a helix formed by three polypeptide chains intertwined with each other, after the temperature rises and dissolves, The gelatin is distributed inside the solution, and plays the role of wrapping the material to be recovered during the cooling process. It has been verified that the effect of adding gelatin in this embodiment is better than that without adding gelatin.

Comparative example 1

Put the chromium picolinate mother liquor in the mother liquor tank for 144 hours, extract the supernatant, recover the chromium picolinate precipitate at the bottom, dry and crush it, the content is 82.53%, after standing for 24 hours, the fluidity is poor, and the product caking reaches 55% , dark purple in color.

The supernatant was evaporated in a vacuum, and the evaporated solid was recovered, dried and crushed, with a content of 4.20 to 12.53%. After standing for 24 hours, the product was agglomerated up to 63%, with poor fluidity and light color.

Different methods of table 1 reclaim the index of chromium picolinate in chromium picolinate mother liquor

group Chromium picolinate content fluidity stability Chromatic aberration Example 1 17.52% good Not easy to agglomerate Consistent color difference Example 7 2.86% good Caking Consistent color difference Comparative example 1 4.20～12.53% Difference Caking Inconsistent color difference

It can be seen from the data in Table 1 that:

The technical solution of the present application can better improve the recovery of chromium picolinate in the chromium picolinate mother liquor through the limitation of a specific process. The product has good fluidity, uniform product content, is not easy to agglomerate, and has consistent color difference. The product picture in Example 1 is shown in Figure 1, the product picture in Example 2 is shown in Figure 2, and the product picture in Comparative Example 1 is shown in Figure 3. It can be drawn from the figure that one of the products of embodiment 1 and embodiment 2 has no caking, and the other has a little caking. These are all products with better effect, and the caking in the comparative example is serious.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. All of them should be covered by the scope of the claims and description of the present invention.

Claims (10)

1. A recovery processing method of chromium picolinate mother liquor is characterized by comprising the following steps:

(1) Adding the carrier into a stirring kettle containing chromium picolinate mother liquor, and stirring uniformly to obtain a solution A;

(2) Adding an anticaking agent into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;

(3) Adding a surfactant into the solution B obtained in the step (2), and uniformly stirring to obtain a solution C;

(4) And (4) sending the solution C obtained in the step (3) to a spray drying tower for spray drying to obtain a chromium picolinate premixed small material product.

2. The method for recycling and treating the chromium picolinate mother liquor as claimed in claim 1, wherein in the step (1), the carrier is more than one of fine silica powder, light calcium carbonate, water-soluble starch, water-soluble maltodextrin and corncob meal.

3. The method for recovering and treating the chromium picolinate mother liquor according to claim 1, wherein in the step (1), the mass ratio of the chromium picolinate to the carrier in the chromium picolinate-containing mother liquor is 1:0.1 to 1000.

4. The method for recycling and treating the chromium picolinate mother liquor as claimed in claim 1, wherein in the step (2), the anticaking agent is one or more of calcium phosphate, microcrystalline cellulose, magnesium stearate, alkyl glycoside 0810 and ferric ammonium citrate.

5. The method for recycling and treating the chromium picolinate mother liquor as claimed in claim 1, wherein in the step (2), the addition amount of the anticaking agent satisfies the following requirements: the mass ratio of the chromium picolinate to the anticaking agent in the mother liquor containing the chromium picolinate is 1:0.01 to 2.

6. The method for recycling and treating the chromium picolinate mother liquor as recited in claim 1, wherein in the step (3), the surface activity is at least one of sodium dodecyl sulfate, alkylphenol ethoxylates and fatty alcohol-polyoxyethylene ethers;

the addition amount of the surfactant satisfies the following conditions: the mass ratio of the chromium picolinate to the surfactant in the mother liquor containing the chromium picolinate is 1:0.0001 to 0.001.

7. The method for recycling and treating the chromium picolinate mother liquor as claimed in claim 1, wherein in the step (4), the inlet air temperature of the spray drying tower is 150-350 ℃ and the outlet air temperature is 100-200 ℃.

8. The method for recovering and treating the chromium picolinate mother liquor as claimed in claim 1, wherein in the step (4), the temperature of the air at the inlet of the spray drying tower is 300 ℃ and the temperature of the air at the outlet of the spray drying tower is 120 ℃.

9. The method for recycling and treating the chromium picolinate mother liquor as claimed in claim 1, wherein in the step (3), the surfactant is added, the mixture is uniformly stirred, then the gelatin is added, the temperature of the solution is raised to 50 ℃, the solution is maintained for 1-2 hours, and then the temperature is lowered to the normal temperature.

10. The method for recovering and treating the chromium picolinate mother liquor according to claim 9, wherein the gelatin is added in an amount which satisfies the following conditions: the mass ratio of the chromium picolinate to the gelatin is 1:0.01 to 2.

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