CN106987312B - Method for simultaneously dephosphorizing and deacidifying grease - Google Patents
Method for simultaneously dephosphorizing and deacidifying grease Download PDFInfo
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Abstract
The invention discloses a method for simultaneously dephosphorizing and deacidifying grease, which comprises the steps of fully contacting the grease to be treated with chelating resin, and removing phospholipid by a hydro-chemical dephosphorization method to obtain the grease after dephosphorization and deacidification. The method achieves the effects of simultaneously dephosphorizing and deacidifying the grease by only one working section, and the process is more compact; compared with the traditional alkali-refining deacidification process, the method is non-alkali-refining deacidification, does not generate saponification side reaction of neutral oil, does not form soapstock, avoids the loss of the neutral oil due to entrainment of the soapstock, and improves the yield of the neutral oil; compared with the SOFT dephosphorization process, the resin can be recycled after being regenerated by cheap acid and alkali, and the operation process does not need to add an emulsifier and carry out strong mechanical stirring or shearing; in a word, compared with the prior art, the method has the advantages of short process flow, simple operation, low cost and remarkable dephosphorization and deacidification effects.
Description
Technical Field
The invention belongs to the technical field of oil refining, relates to a method for simultaneously dephosphorizing and deacidifying oil, and particularly relates to a method for simultaneously dephosphorizing and deacidifying oil by using chelate resin.
Background
Crude oil refers to oil which is directly squeezed or extracted from oil crops and is not subjected to subsequent refining processing, and the main component of the crude oil is a mixture of fatty acid triglycerides (namely, neutral oil). In addition, the crude oil contains other substances such as phospholipids, metal ions, Free Fatty Acids (FFA), proteins, pigments, and water, and the presence of these impurities causes problems such as oxidative deterioration of fats and oils and a shortened storage period, and therefore, it is necessary to remove them by refining fats and oils.
In addition, because phosphorus in the biodiesel can poison a diesel engine exhaust catalyst and increase the emission of pollutants, the phosphorus content in the biodiesel is limited in countries and regions such as the United states, European Union, Brazil and the like, and the national standard GB/T20828 2015 (biodiesel for diesel fuel blending (BD100)) of China also brings the detection of phosphorus into the factory batch inspection project, and the phosphorus content of a final product is required to be less than or equal to 10 mg/kg. It can be seen that the phosphorus content of the grease has an important influence on the final phosphorus content of the biodiesel as a direct raw material of the biodiesel, and therefore, the requirement on grease dephosphorization is also provided.
The common oil refining process comprises the steps of dephosphorization, deacidification (namely alkali refining), decoloration, deodorization, dewaxing and the like. The dephosphorization and deacidification are important processes in the oil refining process, and the cost accounts for more than 90% of the whole oil refining process.
Phospholipid is a natural surfactant, and the loss of neutral oil in the alkali refining process is increased due to the emulsification of the phospholipid if the oil is directly deacidified, so that the removal of the phospholipid, namely a dephosphorization section, is usually the first step of crude oil refining. Phospholipids in oils and fats can be classified into Hydrated Phospholipids (HP) and non-hydrated phospholipids (NHP). Hydrated phospholipid is the majority and has the characteristics of water swelling and aggregation, so the hydrated phospholipid can be removed by a water-adding and centrifugal (or sedimentation) mode, and is industrially called hydrated dephosphorization. The non-hydrated phospholipid mainly comprises undissociated phosphatidic acid, phosphatidic acid or a complex of phosphatidylethanolamine and metal ions such as Ca, Mg, Fe, Cu and the like, the polarity of a polar group of the non-hydrated phospholipid is weak, and the non-hydrated phospholipid cannot be removed by adding water, so that the key point of dephosphorization is how to remove the non-hydrated phospholipid.
Alkali refining deacidification is the most widely used oil deacidification process in industry, which is to neutralize free fatty acid in crude oil by adding aqueous solution of alkaline substances such as sodium hydroxide, calcium hydroxide, sodium carbonate and the like to generate insoluble fatty acid salt (i.e. soapstock) in oil, and then remove the fatty acid salt and other adsorbed impurities by centrifugation. The main disadvantages of this method are: the generated soapstock inevitably carries a part of neutral oil; ② when the addition amount of alkali is too much or the local concentration is too high due to uneven stirring, the alkali will have saponification reaction with neutral oil, further increasing the loss of neutral oil.
US6015915 discloses a process for dephosphorization of fat (referred to in the art as the SOFT dephosphorization process): adding a chelating agent EDTA aqueous solution into the grease, wherein EDTA can be complexed with metal ions in non-hydrated phospholipid in the grease, so that the non-hydrated phospholipid is converted into hydrated phospholipid, and the hydrated phospholipid is removed by hydration dephosphorization. The process has the following disadvantages: firstly, EDTA with high price cannot be recycled, and the economy is poor; secondly, the dephosphorization effect mainly depends on the dispersion degree of EDTA in grease, so Sodium Dodecyl Sulfate (SDS) must be added and the oil phase and the water phase are fully contacted and dispersed by strong mechanical stirring or shearing to form water-in-oil droplets; and thirdly, the added SDS needs to be removed through a subsequent process.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the method for simultaneously dephosphorizing and deacidifying the grease, which has the advantages of short process flow, simple operation, low cost and remarkable dephosphorization and deacidification effects.
The invention is realized by the following technical scheme:
the invention discloses a method for simultaneously dephosphorizing and deacidifying grease, which comprises the steps of fully contacting the grease to be treated with chelating resin, and removing phospholipid by a hydro-chemical dephosphorization method to obtain the grease after dephosphorization and deacidification;
wherein, the skeleton of the chelating resin is styrene-divinylbenzene, and the functional groups are: -NH- (CH)2COO-)2or-CH2-NH-CH2-PO3 2-。
Preferably, the oil to be treated is vegetable oil or animal oil, such as rapeseed oil, soybean oil, zanthoxylum seed oil, tung oil, palm oil, olive oil, lard, tallow, etc.
Preferably, the sufficient contact is to mix the grease to be treated directly with the chelating resin or to flow the grease to be treated through a column packed with the chelating resin.
Directly mixing the grease with the chelating resin, and specifically operating as follows:
adding chelating resin accounting for 1-10% of the oil mass into the oil to be treated, and shaking in a shaking table at a constant temperature for 5-8 h at the temperature of 60 ℃ and at the speed of 200 r/min.
Preferably, the grease to be treated is passed through a column packed with chelating resin, by the specific operations of: the grease to be treated was continuously passed through a column packed with a chelating resin at a flow rate of 1BV/h, and the effluent was collected at the outlet of the column.
The chelate resin can be regenerated, and the regeneration method comprises the following steps:
1) using distilled water with the volume of 2BV to pass through the column to replace grease in the column, wherein the flow rate is 1BV/h, and the flow direction is from bottom to top;
2) using 1.5-2 BV H10% by volume2SO4Enabling the solution to flow through the column at the flow rate of 2BV/h and in the flow direction from bottom to top;
3) passing distilled water with the volume of 2BV through the column at the flow rate of 2BV/h, wherein the flow direction is from bottom to top;
4) passing a 4% NaOH solution with the volume of 5.5-7 BV through the column at the flow rate of 2BV/h, wherein the flow direction is from bottom to top;
5) passing distilled water with the volume of 2BV through the column at the flow rate of 2BV/h in the flow direction from top to bottom;
6) 2BV of refined oil is used for passing through the column, the water in the column is replaced, the flow rate is 2BV/h, and the flow direction is from top to bottom.
Preferably, the grease to be treated is passed through a column packed with chelating resin, by the specific operations of:
the grease to be treated flows through two columns in sequence, the first column is filled with chelating resin, the second column is filled with chelating resin which is converted into Ca, Mg, Fe or Cu type, the flow rate of the grease flowing through the two columns is 1BV/h, and effluent liquid is collected at the outlet of the columns.
A chelate resin which has been transformed into a Ca, Mg, Fe or Cu type, which transformation method comprises the steps of:
1) filling chelating resin into the column, and using 0.05mol/L Ca (NO) with the volume of 50-60 BV3)2、MgCl2、FeCl3Or CuSO4Enabling the solution to flow through the column at the flow rate of 2BV/h in the flow direction from top to bottom;
2) passing distilled water through the column at a flow rate of 2BV/h in a flow direction from top to bottom until the effluent of the column is neutral and free of Ca2+、Mg2+、Fe3+Or Cu2+Stopping the distilled water passing through the column when the distilled water leaks out;
3) and (3) passing 2BV refined oil through the column, replacing the water in the column, wherein the flow rate is 2BV/h, and the flow direction is from top to bottom, and completing resin transformation for later use.
The chelate resin can be regenerated, and the regeneration method comprises the following steps:
1) using distilled water with the volume of 2BV to pass through the column to replace grease in the column, wherein the flow rate is 1BV/h, and the flow direction is from bottom to top;
2) using 1.5-2 BV H10% by volume2SO4Enabling the solution to flow through the column at the flow rate of 2BV/h and in the flow direction from bottom to top;
3) passing distilled water with the volume of 2BV through the column at the flow rate of 2BV/h, wherein the flow direction is from bottom to top;
4) passing a 4% NaOH solution with the volume of 5.5-7 BV through the column at the flow rate of 2BV/h, wherein the flow direction is from bottom to top;
5) passing distilled water with the volume of 2BV through the column at the flow rate of 2BV/h in the flow direction from top to bottom;
6) using 0.05mol/L Ca (NO) with a volume of 50-60 BV3)2、MgCl2、FeCl3Or CuSO4Enabling the solution to flow through the column at the flow rate of 2BV/h in the flow direction from top to bottom;
7) passing distilled water through the column at a flow rate of 2BV/h in a flow direction from top to bottom until the effluent of the column is neutral and free of Ca2+、Mg2+、Fe3+、Cu2+Stopping the distilled water passing through the column when the distilled water leaks out;
8) 2BV of refined oil is used for passing through the column, the water in the column is replaced, the flow rate is 2BV/h, and the flow direction is from top to bottom.
When the calcium ion in the effluent leaked out and is less than 5ppm, the collection operation is finished.
The hydration dephosphorization method is that softened hot water at 80 ℃ accounting for 5 percent of the volume of grease is added into the grease treated by chelating resin, the mixture is shaken in a shaking table at constant temperature of 80-85 ℃ and 200r/min for 20 min-45 min, and then centrifuged at 8000r/min for 20 min.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a method for simultaneously dephosphorizing and deacidifying grease, which comprises the steps of fully contacting the grease to be treated with chelating resin, and removing phospholipid by a hydro-chemical dephosphorization method to obtain the grease after dephosphorization and deacidification. The method achieves the effects of simultaneously dephosphorizing and deacidifying the grease by only one working section, and the process is more compact; compared with the traditional alkali-refining deacidification process, the method is non-alkali-refining deacidification, does not generate saponification side reaction of neutral oil, does not form soapstock, avoids the loss of the neutral oil due to entrainment of the soapstock, and improves the yield of the neutral oil; compared with the SOFT dephosphorization process, the resin can be reused after being regenerated by cheap acid and alkali, and the operation process does not need to add an emulsifier and carry out strong mechanical stirring or shearing. The invention has the advantages of short process flow, simple operation, low cost and remarkable dephosphorization and deacidification effects.
Further, the invention adopts a two-column method, the chelating resin in the first column mainly converts the non-hydrated phospholipid through chelation, and the chelating resin filled in the second column is a metal type of chelating resin with coordination, and the fixed metal can remove FFA through coordination, namely the second column is specially used for deacidification, so that the deacidification effect is better and more guaranteed.
Drawings
FIG. 1 is a schematic diagram of the coordination dephosphorization and deacidification principle of the present invention.
Detailed Description
The following examples are intended to further illustrate the invention but are not intended to represent the only way to practice the invention and are not intended to be limiting.
In the method of US6015915, EDTA is added to convert non-hydrated phospholipids into hydrated phospholipids by chelating away metal ions, but not by coordination deacidification. This is mainly because EDTA is a hexadentate chelating ligand that can simultaneously provide six coordinating atoms, thereby occupying six empty orbitals of the metal ion, and is not able to further coordinate with the hydroxyl oxygen of Free Fatty Acids (FFA), and therefore does not have the deacidification efficacy. In addition, the added EDTA aqueous solution is in the form of water-in-oil, non-hydrated phospholipid can enter the water drop to act with EDTA through the synergistic effect of hydrated phospholipid, and free fatty acid in the oil phase is difficult to enter the water drop, cannot coordinate with EDTA-metal chelate (EDTA-M) to form the form of EDTA-metal chelate-free fatty acid (EDTA-M-FFA), and therefore does not have deacidification effect.
The principle on which the invention is based is shown in fig. 1.
Taking the chelating resin carrying iminodiacetic acid (IDA) functional groups as an example, the IDA resin can be chelated with Ca, Mg, Fe, Cu and other ions in non-hydrated phospholipid. The resin-metal chelate (IDA-M) obtained in this way produces two effects:
firstly, after metal ions are removed from non-hydrated phospholipid (NHP), the non-hydrated phospholipid (NHP) is converted into Hydrated Phospholipid (HP), and the hydrated phospholipid is removed by subsequent hydration dephosphorization; secondly, the chelated metal can remove Free Fatty Acid (FFA) in the grease through coordination (IDA-M-FFA), thereby achieving the purpose of non-alkali refining deacidification. Therefore, the method can achieve the effect of simultaneously dephosphorizing and deacidifying the grease.
In the invention, the IDA resin has a skeleton of styrene-divinylbenzene, and functional groups of: -NH- (CH)2COO-)2The phospholipid is a strongly hydrophobic lipophilic framework, and free fatty acid in the grease can enter the framework, so that non-hydrated phospholipid and free fatty acid dispersed in neutral oil can react with IDA functional groups, and the aims of dephosphorization and deacidification are fulfilled simultaneously.
Example 1
Application of chelating resin Amberlite IRC748+ hydration dephosphorization in dephosphorization and deacidification experiments of rapeseed crude oil
The method used in this example:
20mL of rapeseed crude oil (phosphorus content: 384.2ppm, acid value: 2.38 mg. KOH/g) was put in a flask, and 2g of Amberlite IRC748 chelate resin (Rohm and Haas Co., U.S.A.) having a functional group of IDA was added. The shake flask was placed in a shaker and shaken at 60 ℃ at a constant temperature of 200r/min for 6 h. Then taking out the oil phase, adding softened hot water of 80 ℃ and 5% vol into the oil phase, and shaking at constant temperature of 80 ℃ and 200r/min for 30 min; and centrifuging at 8000r/min for 20min to obtain refined oil.
The final phosphorus content after treatment was 0.9ppm, the acid value after treatment was 0.08mg KOH/g, and the specific parameters are shown in tables 1 and 4.
Hydration dephosphorization: for comparison, the rapeseed crude oil was directly dephosphorized by hydration. The concrete conditions are as follows:
20mL of rapeseed crude oil was put in a shake flask, and softened hot water was added thereto at 80 ℃ and 5% vol. Shaking at 80 deg.C and 200r/min for 30 min; and centrifuging at 8000r/min for 20min to obtain oil after hydration dephosphorization. The final phosphorus content was 124.6ppm and the acid number was 2.26mg KOH/g, see in particular tables 2 and 4.
And (3) a SOFT dephosphorization process: for comparison, the crude rapeseed oil was subjected to SOFT dephosphorization under the following specific conditions:
adding 20mL of rapeseed crude oil into 100mmol/L EDTA aqueous solution with the temperature of 80 ℃ and the volume of 5%, adding 100mmol/L lauryl sodium sulfate (3.456g), crushing at a high speed for 3min, transferring into a magnetic stirrer, stirring slowly for 1h at the temperature of 80 ℃, and centrifuging at 8000r/min for 20min to obtain the oil dephosphorized by the SOFT process. The final phosphorus content was 12.3ppm and the acid number was 2.03mg KOH/g, see in particular tables 3 and 4.
TABLE 1 treatment of crude rapeseed oil by the Process of the invention (Amberlite IRC748 resin-dephosphorization by hydration)
TABLE 2 treatment of crude rapeseed oil by a hydration dephosphorization process
TABLE 3SOFT dephosphorization Process for rapeseed crude oil
TABLE 4 Deacidification Effect of three methods for treating rapeseed crude oil
Obviously, the method adopted by the invention has obvious advantages, neither hydration dephosphorization nor SOFT dephosphorization has obvious deacidification effect, and only the invention has obvious dephosphorization and deacidification effects at the same time. In addition, the invention is also obviously superior to the direct hydration dephosphorization process in terms of dephosphorization.
GB1536-2004 stipulates that the acid value of first-stage rapeseed oil is less than or equal to 0.2mg KOH/g, the acid value of second-stage rapeseed oil is less than or equal to 0.3mg KOH/g, and the acid values of third-stage rapeseed oil and fourth-stage rapeseed oil are respectively less than or equal to 1.0mg KOH/g and less than or equal to 3.0mg KOH/g. The acid value of the rapeseed crude oil used in the experiment is 2.38, which reaches the standard of the fourth-grade rapeseed oil. The rapeseed crude oil is directly subjected to hydration dephosphorization or EDTA solution dephosphorization, the acid value is basically unchanged, the rapeseed crude oil can reach the standard of first-class rapeseed oil after being treated by the method, and the dephosphorization effect is superior to the hydration dephosphorization.
Example 2
Experiments of dephosphorizing and deacidifying soybean crude oil by chelating resin Amberlite IRC747+ hydration dephosphorization
The method comprises the following steps:
20mL of soybean crude oil (phosphorus content: 126.7ppm, acid value: 2.16 mg. KOH/g) was put in a shaking flask, 1g of Amberlite IRC747 chelate resin (Rohm and Haas, USA) having an aminophosphonic acid as a functional group was added thereto, and the shaking flask was put in a shaking table and shaken at a constant temperature of 60 ℃ and 200r/min for 6 hours. Then taking out the oil phase, adding softened hot water of 5% vol and 80 ℃ into the oil phase, and shaking at constant temperature of 80 ℃ and 200r/min for 30 min; and centrifuging at 8000r/min for 20min to obtain refined oil.
The final phosphorus content after the treatment by the method is 0.8ppm, the acid value after the treatment is 0.39mg KOH/g, and the specific parameters are shown in tables 5 and 8.
Hydration dephosphorization: for comparison, crude soybean oil was directly dephosphorized by hydration. The concrete conditions are as follows:
20mL of crude soybean oil was put in a shaking flask, and softened hot water was added thereto at 80 ℃ and 5% vol. Shaking at 80 deg.C and 200r/min for 30 min; and centrifuging at 8000r/min for 20min to obtain oil after hydration dephosphorization. The final phosphorus content was 43.0ppm and the acid number was 2.03mg KOH/g, see in particular tables 6 and 8.
And (3) a SOFT dephosphorization process: for comparison, the crude soybean oil was subjected to SOFT dephosphorization under the following specific conditions:
adding 100mmol/L EDTA aqueous solution of 5% vol at 80 deg.C into 20mL soybean crude oil, adding 100mmol/L sodium dodecyl sulfate (3.456g), crushing at high speed for 3min, transferring into magnetic stirrer, stirring at 80 deg.C for 1h, and centrifuging at 8000r/min for 20min to obtain oil dephosphorized by SOFT process. The final phosphorus content was 10.2ppm and the acid number was 2.13mg KOH/g, see in particular tables 7 and 8.
TABLE 5 treatment of crude Soybean oil by the Process of the invention (Amberlite IRC747 resin-Hydrophosphorization)
TABLE 6 treatment of crude soybean oil by hydration dephosphorization process
TABLE 7SOFT dephosphorization Process for crude Soybean oil
TABLE 8 Deacidification effect of three methods for treating crude soybean oil
Example 3
Application of chelating resin Amberlite IRC748+ hydration dephosphorization in dephosphorization and deacidification experiments of pepper seed crude oil
20mL of Amberlite IRC748 resin (Rohm and Haas company, USA) is filled into a column (the diameter of the column is 1cm, the length of the column is 25cm), crude prickly ash seed oil (the phosphorus content is 233.5ppm, the acid value is 21mg KOH/g) is continuously pumped into the column, the flow rate is 0.3mL/min, the collection is stopped when the calcium ion leakage concentration at the outlet of the column reaches 2ppm, and 4500mL of prickly ash seed oil is collected together. Taking 100mL of resin-treated pricklyash seed oil, adding softened hot water with the temperature of 80 ℃ and the volume of 5%, and shaking at the constant temperature of 80 ℃ and 200r/min for 30 min; and centrifuging at 8000r/min for 20min to obtain refined oil.
The final phosphorus content after the treatment by the method is 0.5ppm, and the acid value after the treatment is 2.05mg KOH/g.
Regenerating the used resin, wherein the specific process comprises the following steps:
(1) using 40mL of distilled water to pass through the column to replace grease in the column, wherein the flow rate is 0.3mL/min, and the flow direction is from bottom to top;
(2) 30mL of 10% H was used2SO4Enabling the solution to flow through the column at the flow rate of 0.6mL/min and in the flow direction from bottom to top;
(3) flushing the resin with 40mL of distilled water at a flow rate of 0.6mL/min in a flow direction from bottom to top;
(4) using 110mL of 4% NaOH solution to flow through the column, wherein the flow rate is 0.6mL/min, and the flow direction is from bottom to top;
(5) 40mL of distilled water is used for passing through the column, the flow rate is 0.6mL/min, and the flow direction is from top to bottom;
(6) 40mL of refined prickly ash seed oil is used for passing through the column to replace the water in the column, the flow rate is 0.6mL/min, and the flow direction is from top to bottom. And finishing resin regeneration for later use.
Example 4
Application of chelating resin Amberlite IRC747+ hydration dephosphorization in dephosphorization and deacidification experiments of rapeseed crude oil
20mL of Amberlite IRC747 resin (Rohm and Haas company, USA) is loaded on a column (the column diameter is 1cm, the column length is 25cm), rapeseed crude oil (phosphorus content: 384.2ppm, acid value: 2.38 mg. KOH/g) is continuously pumped into the column, the flow rate is 0.3mL/min, and collection is stopped when the calcium ion leakage at the column outlet reaches 3ppm, and 2000mL is collected totally. Adding softened hot water with the temperature of 80 ℃ and the volume of 5% into 100mL of rapeseed oil treated by resin, and shaking for 30min at the constant temperature of 80 ℃ and 200 r/min; and centrifuging at 8000r/min for 20min to obtain refined oil.
The final phosphorus content after the treatment by the method is 0.5ppm, and the acid value after the treatment is 0.12mg KOH/g.
Regenerating the used resin, wherein the specific process comprises the following steps:
(1) using 40mL of distilled water to pass through the column to replace grease in the column, wherein the flow rate is 0.3mL/min, and the flow direction is from bottom to top;
(2) 40mL of 10% H were used2SO4Enabling the solution to flow through the column at the flow rate of 0.6mL/min and in the flow direction from bottom to top;
(3) flushing the resin with 40mL of distilled water at a flow rate of 0.6mL/min in a flow direction from bottom to top;
(4) using 140mL of 4% NaOH solution to flow through the column, wherein the flow rate is 0.6mL/min, and the flow direction is from bottom to top;
(5) 40mL of distilled water is used for passing through the column, the flow rate is 0.6mL/min, and the flow direction is from top to bottom;
(6) 40mL of refined rapeseed oil is used for passing through the column to replace the water in the column, the flow rate is 0.6mL/min, and the flow direction is from top to bottom. And finishing resin regeneration for later use.
Example 5
Application of chelating resin Amberlite IRC747+ hydration dephosphorization in dephosphorization and deacidification experiments of palm oil crude oil
20mL of Amberlite IRC747 resin (Rohm and Haas company, USA) are respectively loaded into two columns (the column diameter is 1cm, the column length is 25cm), wherein the ion type of the resin in the second column is Cu type, and the specific transformation process is as follows:
(1) passing 1000mL of 0.05mol/L CuSO4 solution through the column at a flow rate of 0.6mL/min in a flow direction from top to bottom;
(2) passing distilled water through the column at a flow rate of 0.6mL/min in a flow direction from top to bottom until the effluent of the column is neutral and free of Ca2+、Mg2+、Fe3+、Cu2+Stopping the distilled water passing through the column when the distilled water leaks out;
(3) 40mL of refined palm oil was passed through the column to displace the water in the column at a flow rate of 0.6mL/min, with the flow direction being from top to bottom. Continuously pumping crude palm oil (phosphorus content: 56ppm, acid value: 3.5 mg. KOH/g) into two columns in sequence, wherein the flow rate is 0.3mL/min, stopping collection when calcium ions leak out of the column outlet of the second column to reach 1ppm, and collecting 10000mL in total. Taking 100mL of resin-treated palm oil, adding softened hot water with the temperature of 80 ℃ and the volume of 5%, and shaking at the constant temperature of 80 ℃ and 200r/min for 30 min; and centrifuging at 8000r/min for 20min to obtain refined oil.
The final phosphorus content after the treatment by the method is 0.05ppm, and the acid value after the treatment is 0.02mg KOH/g.
Regenerating the used resin, wherein the specific process comprises the following steps:
regeneration of the resin in the first column:
(1) using 40mL of distilled water to pass through the column to replace grease in the column, wherein the flow rate is 0.3mL/min, and the flow direction is from bottom to top;
(2) 40mL of 10% H were used2SO4Enabling the solution to flow through the column at the flow rate of 0.6mL/min and in the flow direction from bottom to top;
(3) flushing the resin with 40mL of distilled water at a flow rate of 0.6mL/min in a flow direction from bottom to top;
(4) using 140mL of 4% NaOH solution to flow through the column, wherein the flow rate is 0.6mL/min, and the flow direction is from bottom to top;
(5) 40mL of distilled water is used for passing through the column, the flow rate is 0.6mL/min, and the flow direction is from top to bottom;
(6) 40mL of refined palm oil was passed through the column to displace the water in the column at a flow rate of 0.6mL/min, with the flow direction being from top to bottom. And finishing resin regeneration for later use.
Regeneration mode of the second column:
firstly, 40mL of distilled water is used for passing through a column to replace grease in the column, the flow rate is 0.6mL/min, and the flow direction is from bottom to top;
② 40mL of 10% H2SO4Enabling the solution to flow through the column at the flow rate of 0.6mL/min and in the flow direction from bottom to top;
thirdly, using distilled water with the volume of 40mL to pass through the column, wherein the flow rate is 0.6mL/min, and the flow direction is from bottom to top;
fourthly, 140mL of 4 percent NaOH solution is used for passing through the column, the flow rate is 0.6mL/min, and the flow direction is from bottom to top;
using 40mL of distilled water to pass through the column, wherein the flow rate is 0.6mL/min, and the flow direction is from top to bottom;
sixthly, 1000mL of 0.05mol/L Ca (NO) is used3)2、MgCl2、FeCl3Or CuSO4Enabling the solution to flow through the column at the flow rate of 0.6mL/min in a flow direction from top to bottom;
seventhly, distilled water is used for flowing through the column at the flow rate of 0.6mL/min, the flow direction is from top to bottom until the effluent liquid of the column is neutral and has no Ca2+、Mg2+、Fe3+Or Cu2+Stopping the distilled water passing through the column when the distilled water leaks out;
and allowing 2BV refined palm oil to pass through the column, displacing water in the column, controlling the flow rate to be 2BV/h, and completing resin regeneration from top to bottom in the flow direction for later use.
Claims (10)
1. A method for simultaneously dephosphorizing and deacidifying grease is characterized in that grease to be treated is fully contacted with chelating resin, and phospholipid is removed by a hydro-chemical dephosphorization method to obtain the grease after dephosphorization and deacidification;
wherein, the skeleton of the chelating resin is styrene-divinylbenzene, and the functional groups are: -NH- (CH)2COO-)2or-CH2-NH-CH2-PO3 2-。
2. The method for simultaneously dephosphorizing and deacidifying fat and oil according to claim 1, wherein said sufficient contact is to directly mix the fat and oil to be treated with chelating resin or to flow the fat and oil to be treated through a column packed with chelating resin.
3. The method for simultaneously dephosphorizing and deacidifying grease according to claim 2, wherein the grease is directly mixed with chelating resin by the following specific operations:
adding chelating resin accounting for 1-10% of the oil mass into the oil to be treated, and shaking in a shaking table at a constant temperature for 5-8 h at the temperature of 60 ℃ and at the speed of 200 r/min.
4. The method for simultaneously dephosphorizing and deacidifying fat and oil according to claim 2, wherein the fat and oil to be treated is passed through the column filled with chelating resin by the following specific operations:
the grease to be treated was continuously passed through a column packed with a chelating resin at a flow rate of 1BV/h, and the effluent was collected at the outlet of the column.
5. The method for simultaneously dephosphorizing and deacidifying grease and oil according to claim 4, wherein said chelating resin can be regenerated, the regeneration method comprises the following steps:
1) using distilled water with the volume of 2BV to pass through the column to replace grease in the column, wherein the flow rate is 1BV/h, and the flow direction is from bottom to top;
2) using 1.5-2 BV H10% by volume2SO4Enabling the solution to flow through the column at the flow rate of 2BV/h and in the flow direction from bottom to top;
3) passing distilled water with the volume of 2BV through the column at the flow rate of 2BV/h, wherein the flow direction is from bottom to top;
4) passing a 4% NaOH solution with the volume of 5.5-7 BV through the column at the flow rate of 2BV/h, wherein the flow direction is from bottom to top;
5) passing distilled water with the volume of 2BV through the column at the flow rate of 2BV/h in the flow direction from top to bottom;
6) 2BV of refined oil is used for passing through the column, the water in the column is replaced, the flow rate is 2BV/h, and the flow direction is from top to bottom.
6. The method for simultaneously dephosphorizing and deacidifying fat and oil according to claim 2, wherein the fat and oil to be treated is passed through the column filled with chelating resin by the following specific operations:
the grease to be treated flows through two columns in sequence, the first column is filled with chelating resin, the second column is filled with chelating resin which is converted into Ca, Mg, Fe or Cu type, the flow rate of the grease flowing through the two columns is 1BV/h, and effluent liquid is collected at the outlet of the columns.
7. The method for simultaneously dephosphorizing and deacidifying fat and oil according to claim 6, wherein said chelating resin has been transformed into Ca, Mg, Fe or Cu type, and said transformation method comprises the following steps:
1) filling chelating resin into the column, and using 0.05mol/L Ca (NO) with the volume of 50-60 BV3)2、MgCl2、FeCl3Or CuSO4Enabling the solution to flow through the column at the flow rate of 2BV/h in the flow direction from top to bottom;
2) passing distilled water through the column at a flow rate of 2BV/h in a flow direction from top to bottom until the effluent of the column is neutral and free of Ca2+、Mg2+、Fe3+Or Cu2+Stopping the distilled water passing through the column when the distilled water leaks out;
3) and (3) passing 2BV refined oil through the column, replacing the water in the column, wherein the flow rate is 2BV/h, and the flow direction is from top to bottom, and completing resin transformation for later use.
8. The method for simultaneously dephosphorizing and deacidifying grease according to claim 6, wherein said chelating resin can be regenerated, the regeneration method comprising the steps of:
1) using distilled water with the volume of 2BV to pass through the column to replace grease in the column, wherein the flow rate is 1BV/h, and the flow direction is from bottom to top;
2) using 1.5-2 BV H10% by volume2SO4Enabling the solution to flow through the column at the flow rate of 2BV/h and in the flow direction from bottom to top;
3) passing distilled water with the volume of 2BV through the column at the flow rate of 2BV/h, wherein the flow direction is from bottom to top;
4) passing a 4% NaOH solution with the volume of 5.5-7 BV through the column at the flow rate of 2BV/h, wherein the flow direction is from bottom to top;
5) passing distilled water with the volume of 2BV through the column at the flow rate of 2BV/h in the flow direction from top to bottom;
6) using 0.05mol/L Ca (NO) with a volume of 50-60 BV3)2、MgCl2、FeCl3Or CuSO4Enabling the solution to flow through the column at the flow rate of 2BV/h in the flow direction from top to bottom;
7) passing distilled water through the column at a flow rate of 2BV/h in a flow direction from top to bottom until the effluent of the column is mediumIs neutral and free of Ca2+、Mg2+、Fe3+、Cu2+Stopping the distilled water passing through the column when the distilled water leaks out;
8) 2BV of refined oil is used for passing through the column, the water in the column is replaced, the flow rate is 2BV/h, and the flow direction is from top to bottom.
9. The method for simultaneous dephosphorization and deacidification of fats and oils according to claim 4 or 6, wherein the collecting operation is ended when calcium ions are leaked out and less than 5ppm in the effluent.
10. The method for simultaneously dephosphorizing and deacidifying fat and oil according to claim 1, wherein the method for dephosphorizing and dephosphorizing fat and oil comprises adding softened hot water at 80 ℃ accounting for 5% of the volume of the fat and oil into the fat and oil treated by chelating resin, shaking the mixture in a shaking table at a constant temperature of 80-85 ℃ and 200r/min for 20-45 min, and centrifuging the mixture for 20min at 8000 r/min.
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