Method for high-yield extraction of high-acid-value crude tall oil from saponified product

Abstract

The invention provides a method for high-yield extraction of high-acid-value crude tall oil from saponified matter, and the method comprises the following steps: adding a composite washing liquid into an upper-layer substance separated after the saponified matter is subjected to sedimentation treatment, stirring and standing, the composite washing liquid being composed of water, acidification waste liquid, sodium sulfate, sodium hydroxide and a surfactant; raising the temperature of the upper-layer material after standing, adding an acidic material, raising the temperature to 100-120 DEG C again, and keeping the temperature; and adding an auxiliary agent, uniformly stirring, standing at the temperature of 70-95 DEG C, and stirring at a low speed to obtain an upper-layer product, namely crude tall oil. According to the method, the yield of the crude tall oil is increased, the acid value of the crude tall oil is increased, generation of acidification waste liquid in the acidification process is reduced, and the method has high application value and market competitiveness.

Description

Technical Field

[0001] The present invention relates to the technical field of petrochemical engineering, and particularly to a method for extracting crude tall oil with a high acid value in a high yield from saponified matter. Background Art

[0002] In the field of petrochemical engineering, the extraction of saponified matter is a key process step, mainly used for recovering high-value-added chemicals from petroleum by-products. As an important chemical raw material, crude tall oil is widely used in industries such as synthetic detergents, textile auxiliaries, and pesticide emulsifiers. However, its extraction process is complex, and the yield is easily affected by impurities such as lignin.

[0003] Currently, the extraction of crude tall oil mainly relies on organic solvents or water as washing liquids. For example, hot water or alkaline solutions are used to remove impurities such as lignin. In addition, acidification treatment (such as using hydrochloric acid or sulfuric acid) can change the chemical properties of saponified matter, thereby increasing the yield of crude tall oil. These methods have optimized the extraction efficiency to a certain extent. However, it is difficult to completely remove impurities such as lignin during the washing process, resulting in a decrease in the yield of crude tall oil. At the same time, although acidification treatment can increase the yield, it may be accompanied by a decrease in the acid value, affecting the product quality. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method for extracting crude tall oil with a high acid value in a high yield from saponified matter, increasing the yield of crude tall oil and having a relatively high acid value, so as to solve the above technical problems existing in the prior art.

[0005] The present invention is implemented by adopting the following technical solutions:

[0006] A method for extracting crude tall oil with a high acid value in a high yield from saponified matter, comprising the following steps:

[0007] (1) Adding a composite washing liquid to the upper layer substance separated after the saponified matter undergoes sedimentation treatment, stirring and then standing still. The composite washing liquid is composed of water, acidified waste liquid, sodium sulfate, sodium hydroxide, and a surfactant;

[0008] (2) Heating the upper layer substance after standing still and then adding an acidic substance, and then heating to 100 - 120 °C for heat preservation;

[0009] (3) Adding an auxiliary agent and stirring evenly, then standing still at a temperature of 70 - 95 °C with low-speed stirring. The upper layer product is crude tall oil.

[0010] The inventor unexpectedly found that by using a composite washing liquid in the present invention and adding a surfactant to enhance the separation effect between lignin and saponified matter, the vast majority of lignin can be separated from saponified matter. In addition, most of the acidified waste liquid is used as a component of the washing liquid in the present invention, greatly reducing the treatment of acidified waste liquid in the later stage.

[0011] As a further solution of the present invention: in step (1), the time for sedimentation treatment is 1 to 6 h, and the temperature is 40 to 65 °C;

[0012] And / or, in step (1), the addition amount of the composite washing liquid is 0.8 to 1.3 times the weight of the saponified product.

[0013] As a further solution of the present invention: in step (1), the weight fractions of the components in the composite washing liquid are as follows: 30 to 50 parts of water, 30 to 50 parts of acidified waste liquid, 5 to 10 parts of sodium sulfate, 5 to 10 parts of sodium hydroxide, and 1 to 2 parts of surfactant.

[0014] As a further solution of the present invention: the acidified waste liquid is the lower layer liquid obtained by high-temperature standing after acidification of the saponified product;

[0015] The surfactant is selected from one of fatty acid, oleic acid, lauric acid, and sodium fatty acid methyl ester sulfonate.

[0016] As a further solution of the present invention: in step (1), the temperature of the stirring is 40 to 60 °C, the time is 0.5 to 2 h, and the speed is 500 to 1500 r / min.

[0017] As a further solution of the present invention: in step (1), the time for standing is 1.5 to 6 h, and the temperature is 40 to 60 °C.

[0018] As a further solution of the present invention: in step (2), the temperature for heating the upper layer substance after standing is 50 to 70 °C;

[0019] And / or, in step (2), the acidic substance is one or two of acetic acid, hydrochloric acid, sulfuric acid, and nitric acid;

[0020] And / or, the addition amount of the acidic substance is 5 to 15% of the weight of the saponified product.

[0021] As a further solution of the present invention: in step (2), the time for heat preservation is 0.5 to 2 h.

[0022] As a further solution of the present invention: in step (3), the auxiliary agent is at least one of sodium lignin sulfonate, calcium lignin sulfonate, carboxymethyl cellulose, and carboxyethyl cellulose;

[0023] The addition amount of the auxiliary agent is 1 to 3% of the weight of the saponified product.

[0024] As a further solution of the present invention: in step (3), the time for standing is 6 to 10 h, and the speed of the low-speed stirring is 5 to 15 r / min.

[0025] The beneficial effects of the present invention are as follows:

[0026] 1. Significantly improve the washing efficiency: Due to the single ratio, the washing efficiency of traditional washing solutions is relatively low. The present invention adopts a multi-component formula and optimizes the separation effect by adding surfactants to ensure the efficient separation of lignin and saponified substances. At the same time, the acidified waste liquid is used as a component of the washing liquid, greatly reducing the subsequent waste liquid treatment cost and significantly improving the washing efficiency.

[0027] 2. Increase the yield and economic value of crude tall oil: The oil-wood mixture produced by traditional crude tall oil extraction methods has high viscosity and is difficult to separate, and is mostly sold as low-end products, making it difficult to reflect the value of the components. The present invention significantly reduces the generation of the oil-wood mixture through process optimization, while increasing the yield of crude tall oil, further enhancing the economic value of the product.

[0028] 3. Improve the acid value and application potential of crude tall oil: Due to incomplete separation of lignin in traditional methods, the acid value of crude tall oil is relatively low, affecting its subsequent application value. The present invention ensures a significant increase in the acid value of crude tall oil through optimized separation processes, providing a better-quality raw material for high-value-added applications such as subsequent rectification, and further enhancing the market competitiveness of the product.

[0029] In summary, the method for extracting crude tall oil from saponified substances of the present invention has achieved significant improvements in terms of washing efficiency, crude tall oil yield, and acid value. At the same time, it effectively reduces the generation of acidified waste liquid, and has outstanding application value and market competitiveness. Detailed implementation manners

[0030] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples and do not limit the scope of the present invention. Those skilled in the art can think of other obvious variations. The basic principles defined in the following description can be applied to other implementation schemes, variant schemes, improvement schemes, equivalent schemes, and other technical schemes that do not deviate from the spirit and scope of the present invention.

[0031] For the instruments or raw materials in the present invention that are not specified by the manufacturer, they are all conventional commercial instruments or raw materials.

[0032] For the detection indicators involved in the embodiments of the present invention that are not mentioned, they are all detected using conventional detection methods in the art.

[0033] Example 1

[0034] Step 1: Take 500 g of saponified substances. Place the saponified substances at 40°C and let them stand for 6 h, separate the lower black liquor, and obtain the upper sedimented saponified substances.

[0035] Step 2: Prepare the washing solution. The components of the washing solution are 140 g of water, 180 g of acidified waste liquid, 40 g of sodium sulfate, 32 g of sodium hydroxide, and 8 g of oleic acid. Mix the washing solution with the saponified product after sedimentation in a reaction kettle, and stir at 50 °C and 1000 r / min for 1 h. Then let it stand at 50 °C for 1.5 h, separate the lower-layer liquid, and keep the upper-layer saponified product after washing.

[0036] Step 3: Heat the saponified product after washing in the kettle to 65 °C, add 50 g of sulfuric acid, and keep it at 110 °C for 2 h. Then add 10 g of sodium lignosulfonate and stir evenly.

[0037] Step 4: Let the acidified sample stand at 85 °C for 10 h, and control the stirring speed at 5 r / min.

[0038] Step 5: Separate the oil and liquid of the well-settled and separated sample. The upper layer is Sample 1. Obtain 1221 g of Sample 1.

[0039] Example 2

[0040] Step 1: Take 500 g of saponified product. Place the saponified product at 55 °C and let it stand for 2 h, separate the lower-layer black liquor, and obtain the upper-layer sedimented saponified product.

[0041] Step 2: Prepare the washing solution. The components of the washing solution are 200 g of water, 150 g of acidified waste liquid, 45 g of sodium sulfate, 30 g of sodium hydroxide, and 5 g of oleic acid. Mix the washing solution with the saponified product after sedimentation in a reaction kettle, and stir at 55 °C and 1100 r / min for 1.5 h. Then let it stand at 60 °C for 2 h, separate the lower-layer liquid, and keep the upper-layer saponified product after washing.

[0042] Step 3: Heat the saponified product after washing in the kettle to 70 °C, add 20 g of sulfuric acid and 35 g of nitric acid, and keep it at 105 °C for 1.5 h. Then add 12 g of calcium lignosulfonate and stir evenly.

[0043] Step 4: Let the acidified sample stand at 90 °C for 6 h, and control the stirring speed at 7 r / min.

[0044] Step 5: Separate the oil and liquid of the well-settled and separated sample. The upper layer is Sample 2. Obtain 2225 g of Sample 2.

[0045] Example 3

[0046] Step 1: Take 500 g of saponified product. Place the saponified product at 65 °C and let it stand for 1 h, separate the lower-layer black liquor, and obtain the upper-layer sedimented saponified product.

[0047] Step 2: Configure the washing solution. The components of the washing solution are 250 g of water, 300 g of acidified waste liquid, 50 g of sodium sulfate, 40 g of sodium hydroxide, and 10 g of oleic acid. Mix the washing solution with the saponified product after sedimentation in a reaction kettle, stir at 60 °C and 600 r / min for 2 h. Then let it stand at 50 °C for 6 h, separate the lower layer of liquid, and keep the upper layer of saponified product after washing.

[0048] Step 3: Heat the saponified product after washing in the kettle to 50 °C, add 35 g of acetic acid and 30 g of hydrochloric acid, and keep it at 120 °C for 1 h. Then add 6 g of carboxymethyl cellulose and 6 g of carboxyethyl cellulose, and stir evenly.

[0049] Step 4: Let the acidified sample stand at 95 °C for 6 h, and control the stirring speed at 10 r / min.

[0050] Step 5: Separate the oil and liquid of the well-separated sample by standing. The upper layer is Sample 3. 2223 g of Sample 3 is obtained.

[0051] Comparative Example 1

[0052] The difference from Example 1 is that the detergent used is 400 g of Na 2 SO 4 aqueous solution with a concentration of 15 °Be, and 4162 g of Sample 4 is obtained.

[0053] Comparative Example 2

[0054] The difference from Example 1 is that oleic acid is not added to the washing solution, and 173 g of Sample 5 is obtained.

[0055] Application Examples

[0056] Use the methods of DB 53 / T 579-2014 "Tall Oil" and DB43 / T 1663-2002 "Determination of Acid Value of Tall Oil Extracted from Black Liquor" to measure the solid content and acid value of the products of Examples 1 to 3 and Comparative Examples 1 to 3. The specific test results are shown in the table.

[0057] Number Solid Content (%) Acid Value (g / mg) Yield (%) Example 1 96.34 152.23 44.2 Example 2 97.13 153.36 45 Example 3 95.56 153.72 44.6 Comparative Example 1 94.36 126.25 32.4 Comparative Example 2 95.28 130.58 34.6

[0058] It can be seen from the above test results that: the method of the present application improves the yield of crude tall oil, increases the acid value of crude tall oil, reduces the generation of acidified waste liquid during the acidification process, and has high application value and market competitiveness.

[0059] The foregoing has shown and described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments, and what is described in the above embodiments and the specification only illustrates the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements fall within the scope of the present invention claimed. The scope of the present invention claimed is defined by the appended claims and their equivalents.

Claims

1. A method for extracting high-acid crude tall oil from saponified products with high yield, characterized in that: The steps include: (1) adding a composite washing liquid to the upper layer of the saponified product separated after sedimentation, stirring and then standing, wherein the composite washing liquid is composed of water, acidified waste liquid, sodium sulfate, sodium hydroxide and a surfactant; (2) heating the upper layer after standing, adding an acidic substance, and heating it again to 100-120°C for insulation; (3) After adding the auxiliary agent and stirring evenly, the mixture is allowed to stand at a temperature of 70 to 95°C with slow stirring. The upper layer product is crude tar oil.

2. The method for extracting high-acid value crude tall oil from saponified product according to claim 1, characterized in that: In step (1), the sedimentation treatment time is 1 to 6 hours and the temperature is 40 to 65° C.; And / or, in step (1), the added amount of the composite washing liquid is 0.8 to 1.3 times the weight of the saponified product.

3. The method for extracting high-acid value crude tall oil from saponified product in high yield according to claim 2, characterized in that: In step (1), the weight fractions of the components in the composite washing liquid are as follows: 30-50 parts of water, 30-50 parts of acidified waste liquid, 5-10 parts of sodium sulfate, 5-10 parts of sodium hydroxide, and 1-2 parts of surfactant.

4. The method for extracting high-acid value crude tall oil from saponified product in high yield according to claim 3, characterized in that: The acidified waste liquid is the lower layer of liquid left to stand at high temperature after the saponified product is acidified; And / or, the surfactant is selected from one of fatty acid, oleic acid, lauric acid and sodium fatty acid methyl ester sulfonate.

5. The method for extracting high-acid value crude tall oil from saponified product with high yield according to claim 1, characterized in that: In step (1), the stirring temperature is 40-60° C., the time is 0.5-2 h, and the speed is 500-1500 r / min.

6. The method for extracting high-acid value crude tall oil from saponified product with high yield according to claim 1, characterized in that: In step (1), the standing time is 1.5 to 6 hours and the temperature is 40 to 60°C.

7. The method for extracting high-acid-value crude tall oil from saponified product with high yield according to claim 1, characterized in that: In step (2), the temperature of the upper layer after standing is raised to 50-70°C; And / or, in step (2), the acidic substance is one or two of acetic acid, hydrochloric acid, sulfuric acid, and nitric acid; And / or, in step (2), the amount of the acidic substance added is 5-15% of the weight of the saponified product.

8. The method for extracting high-acid-value crude tall oil from saponified product with high yield according to claim 1, characterized in that: In step (2), the insulation time is 0.5 to 2 hours.

9. The method for extracting high-acid-value crude tall oil from saponified product in high yield according to claim 1, characterized in that: In step (3), the auxiliary agent is at least one of sodium lignin sulfonate, calcium lignin sulfonate, carboxymethyl cellulose and carboxyethyl cellulose; And / or, the additive amount of the auxiliary agent is 1-3% of the weight of the saponified product.

10. The method for extracting high-acid-value crude tall oil from saponified product with high yield according to claim 1, characterized in that: In step (3), the standing time is 6 to 10 hours, and the low-speed stirring speed is 5 to 15 r / min.