Preparation method of rosin resin acid

Abstract

The invention relates to the technical field of deep processing of rosin resin acid, in particular to a preparation method of rosin resin acid. According to the specific technical scheme, the preparation method of the rosin resin acid comprises the following steps: adding a carrying agent into rosin, dissolving, and carrying out ultrasonic oscillation and filtration; adding the filtrate into a supercritical extraction kettle, pumping CO2 cooling liquid, and maintaining the pressure; after pressure maintaining is completed, the CO2 liquid enters the separation kettle and is heated into gas, the gas enters the gas collection device, and an extract, namely the rosin resin acid, is obtained in the separation kettle. The preparation method disclosed by the invention is environment-friendly, green, non-toxic and cheap; the process is simple, rosin is fully impregnated under high-pressure CO2, extraction is performed in an extraction kettle-extraction kettle-separation kettle-separation kettle continuous extraction mode, the extraction rate of target components is increased, more than 80% of rosin resin acid can be reserved, and the extraction rate of the rosin resin acid is greatly increased.

Description

Technical Field

[0001] The invention relates to the technical field of deep processing of rosin resin acid, and in particular to a preparation method of rosin resin acid. Background Art

[0002] Rosin resin acid is a tricyclic diterpene oxygen-containing compound and one of the most important resin acids. Its main production methods are steam distillation, vacuum fractionation and extraction-fractionation. Rosin resin acid contains abietic acid as the main component (about 50%), and also contains multiple abietic isomers, such as levorotatory pimaric acid, neoabietic acid, longifolia abietic acid, etc., collectively referred to as rosin resin acid below. More and more research on rosin and rosin resin acid has expanded its further application in many fields. As a type of non-petrochemical natural resource, rosin resin acid has the advantages of a wide source of raw materials, renewable, and easy degradation of products. It is an environmentally friendly green material.

[0003] Resin acid contains fewer impurities and can be used to prepare rosin deep processing upgraded products with higher added value. At present, there are many studies on the separation of resin acid from rosin; rosin is a solid resin crystal obtained after distillation of rosin, which is composed of several isomers of resin acid (such as abietic acid, levorotatory pimaric acid, dehydroabietic acid, long-leaved palustric acid, etc.), among which rosin is the oleoresin in the wood of Pinus massoniana, Pinus tabulaeformis or other plants of the same genus. Methods for obtaining resin acid crystals include natural cooling crystallization, water cooling crystallization, and organic solvent (dichloromethane, acetonitrile, acetone and ethyl acetate) dissolution precipitation method. The natural cooling crystallization method takes a long time, and the resulting crystals are less and of low purity, but the energy consumption is low. The water cooling crystallization method takes less time and obtains more crystals, but it consumes water and requires water cooling equipment, which increases energy consumption and investment. Solvents such as acetone, dichloromethane and acetonitrile are volatile and have certain toxicity, which will pollute the environment and are not conducive to industrial promotion and application. In ethyl acetate, rosin resin acid reacts with butanolamine to generate a polyacrylamide precipitate with large particle size, low viscosity, easy to filter and wash. The crude amine salt product obtained by filtration has less solvent residue, light color and good dispersibility; however, this method has complicated steps, requires more samples and costs. However, there are few studies on directly obtaining resin acid from rosin without distillation. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention provides a method for preparing rosin resin acid, which solves the problems of low extraction rate and high extraction cost in the prior art extraction process, which are not conducive to the promotion and use of rosin resin acid.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions: The invention discloses a method for preparing rosin resin acid. The preparation process comprises the following steps: adding a carrier into rosin, dissolving the carrier, and filtering the carrier after ultrasonic vibration; adding the filtrate into a supercritical extraction kettle, and pumping CO2 coolant into the kettle to maintain the pressure; after the pressure maintenance is completed, the CO2 liquid enters a separation kettle, is heated to be gas, and enters a gas collecting device, and an extract is obtained in the separation kettle, namely, the rosin resin acid.

[0006] Preferably, the carrying agent is a reagent that can dissolve rosin resin acid.

[0007] Preferably, the carrying agent is at least one of n-butanol, n-propanol, ethanol, methanol and acetone.

[0008] Preferably, the mass ratio of the rosin to the carrying agent is 1:5 to 1:50.

[0009] Preferably, the molar fraction of the carrying agent in CO2 is 5% to 35%.

[0010] Preferably, in the extraction kettle, the pressure is 10 MPa to 45 MPa, and the temperature is 313.15 K to 348.15 K.

[0011] Preferably, the holding time is 30 min to 80 min.

[0012] The present invention has the following beneficial effects: 1. The present invention combines supercritical extraction with a traditional rosin resin acid purification process, and through an extraction kettle and a separation kettle, the conditions and parameters such as the type of the carrier, the gas pressure in the kettle, the gas flow rate, the extraction time and the extraction temperature are adjusted, and a continuous extraction method of extraction kettle-extraction kettle-separation kettle-separation kettle is adopted to realize supercritical CO2 extraction of rosin resin acid, and the operating temperature is low, the process is safe, and there is no organic solvent residue, so that the rosin resin acid in the rosin is extracted to the maximum extent.

[0013] 2. The present invention obtains rosin resin acid without residual solvent by regulating temperature and pressure, and has high safety and cost. The preparation method is environmentally friendly, green, non-toxic and inexpensive; the process is simple, rosin is fully impregnated under high-pressure CO2, and the extraction is carried out by continuous extraction of extraction kettle-extraction kettle-separation kettle-separation kettle, which improves the extraction rate of the target component, and the rosin resin acid can be retained by more than 80%, which greatly improves the extraction rate of the rosin resin acid. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is a diagram of the supercritical extraction device for rosin resin acid. DETAILED DESCRIPTION

[0015] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0016] Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

[0017] The invention discloses a method for preparing rosin resin acid, which comprises the following steps: (1) Add a carrier to the rosin, stir and dissolve, place in an ultrasonic oscillator for 5 minutes, filter, and place the filtrate in a refrigerator for later use; the carrier is a reagent that can dissolve rosin resin acid, including but not limited to n-butanol, n-propanol, ethanol, methanol, and acetone. The mass ratio of the rosin to the carrier is 1:5 to 1:50.

[0018] (2) The filtrate is added to the supercritical extraction kettle, the carbon dioxide cylinder is opened, and the carbon dioxide gas is pressurized by a high-pressure pump through a refrigeration device and pumped into the extraction kettle. The pressure is controlled to be 10MPa~45Mpa, the temperature is 313.15K~348.15K, and the pressure is maintained for 30min~80min; the molar fraction of the carrying agent in CO2 is 5%~35%.

[0019] (3) After the pressure maintenance is completed, the valve connecting the extraction kettle and the separation kettle is opened, and the supercritical carbon dioxide fluid enters the separation kettle and is heated to become gas. After passing through the separation kettle, it enters the gas collection device and waits to enter the extraction kettle next time; wherein, the extract remains in the separation kettle, which is rosin resin acid. Among them, the refrigeration device and the gas collection device are both prior art.

[0020] The reaction device used in the present invention is as follows Figure 1 As shown, according to the device, the entire extraction process is: fill the extraction kettle, open the gas cylinder, turn on the refrigeration device at the same time, start the CO2 pump, the CO2 gas fills the extraction kettle, and the gas cools down and becomes liquid under the action of the refrigeration device, that is, the gas CO2 reaches a supercritical state and is fully mixed with the rosin-carrier solution in the extraction kettle, dissolves and takes away the extraction components, and enters the separation kettle. The supercritical carbon dioxide fluid is heated to become CO2 gas and enters the gas collection device from port A, and the extract remains in the separation kettle, completing the extraction and separation. Among them, the number of extraction kettles and separation kettles is set according to needs.

[0021] The present invention will be further described below in conjunction with specific embodiments.

[0022] In the following embodiments, the calculation formula for the extraction rate of rosin resin acid is: ; Where: Y is the extraction rate of rosin resin acid; M1 is the mass of extracted rosin resin acid; M2 is the mass of the fed rosin.

[0023] Example 1 According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml n-butanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 25MPa, the extraction temperature to 323.15K, and the extraction time to be 50min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0024] Example 2 The main difference between this example and Example 1 is that the carrying agent is changed to n-propanol.

[0025] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml of n-propanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 25MPa, the extraction temperature to 323.15K, and the extraction time to be 50min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0026] Example 3 The main difference between this example and Example 1 is that the carrying agent is changed to anhydrous ethanol.

[0027] According to the formula, accurately weigh a certain amount of 5 grams of rosin, add it to 80 ml of anhydrous ethanol (mass fraction is 20%), stir to fully dissolve it and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 25MPa, the extraction temperature to 323.15K, and the extraction time to be 50min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0028] Example 4 The main difference between this example and Example 1 is that the carrying agent is changed to methanol.

[0029] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml methanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for standby use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 25MPa, the extraction temperature to 323.15K, and the extraction time to be 50min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0030] Example 5 The main difference between this example and Example 1 is that the carrying agent is changed to acetone.

[0031] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml acetone (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 25MPa, the extraction temperature to 323.15K, and the extraction time to be 50min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0032] Example 6 The main difference between this example and Example 1 is that the temperature is changed to 333.15K.

[0033] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml n-butanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for standby use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 25MPa, the extraction temperature to 333.15K, and the extraction time to be 50min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0034] Example 7 The main difference between this example and Example 1 is that the temperature is changed to 343.15K.

[0035] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml n-butanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 25MPa, the extraction temperature to 343.15K, and the extraction time to be 50min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0036] Example 8 The main difference between this example and Example 1 is that the pressure is changed to 10 MPa.

[0037] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml n-butanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 10MPa, the extraction temperature to 323.15K, and the extraction time to be 50min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0038] Example 9 The main difference between this example and Example 1 is that the pressure is changed to 35 MPa.

[0039] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml n-butanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 35MPa, the extraction temperature to 323.15K, and the extraction time to be 50min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0040] Example 10 The main difference between this example and Example 1 is that the pressure is changed to 45 MPa.

[0041] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml n-butanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 45MPa, the extraction temperature to be 323.15K, and the extraction time to be 50min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0042] Embodiment 11 The main difference between this example and Example 1 is that the time is changed to 40 minutes.

[0043] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml n-butanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for standby use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 25MPa, the extraction temperature to 323.15K, and the extraction time to be 40min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0044] Example 12 The main difference between this example and Example 1 is that the time is changed to 60 minutes.

[0045] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml n-butanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 25MPa, the extraction temperature to 323.15K, and the extraction time to be 60min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0046] Embodiment 13 The main difference between this example and Example 1 is that the time is changed to 80 minutes.

[0047] According to the formula, accurately weigh a certain amount of rosin 5 grams, add it to 80ml n-butanol (mass fraction is 20%), stir to fully dissolve and prepare a solution, put it in an ultrasonic oscillator for 5 minutes, and put the filtrate in a refrigerator for use. Place the above solution in supercritical extraction kettle 1, open the carbon dioxide cylinder, and the carbon dioxide gas passes through the refrigeration device and is pressurized by a high-pressure pump at a flow rate of 20kg / h before entering extraction kettle 1 and extraction kettle 2. Control the extraction pressure to be constant at 25MPa, the extraction temperature to 323.15K, and the extraction time to 80min; after the extraction is completed, open the valve between extraction kettle 2 and separation kettle 1, and after the CO2 gas passes through the entire device passage, rosin resin acid can be obtained from the separation kettle.

[0048] The extraction rate results of Examples 1 to 13 are shown in Table 1. The results show that the extraction rate of the extraction method of Example 1 of the present invention is the highest. By comparing Examples 1 to 13, it can be seen that the extraction rate changes to varying degrees by changing the extraction method, including the type of carrier, extraction temperature, pressure and time.

[0049] Table 1 Extraction rate results of Examples 1-13 Example Extraction rate (%) Example Extraction rate (%) Example 1 80 Example 8 44 Example 2 73 Example 9 80 Example 3 69 Example 10 80 Example 4 61 Embodiment 11 69 Example 5 56 Example 12 80 Example 6 71 Embodiment 13 80 Example 7 62 The rosin resin acid extracted by the present invention can be used in the fermentation industry and as a filler in the soap and papermaking industries. Oxidized rosin soap salt can be used as a new type of surfactant, has good emulsification power for toluene, and can be used as a low-foaming metal surface cleaning component; dehydroabietic acid has a large specific rotation and is a good pharmaceutical intermediate. Dextrorotatory dehydroabietic acid is used to degrade amines to separate racemic α-phenoxypropionic acid and α-benzyloxycarbonylaminophenylacetic acid, both of which are intermediates for synthesizing penicillin drugs; in addition, rosin resin acid has uses in the material industry, food industry, flavors and fragrances, etc.

[0050] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for preparing rosin resin acid, characterized in that: The preparation process is as follows: adding a carrier to rosin, dissolving it, and filtering it by ultrasonic vibration; adding the filtrate to a supercritical extraction kettle, and pumping in CO2 coolant to maintain the pressure; After the pressure maintenance is completed, the CO2 liquid enters the separation kettle and is heated to gas and enters the gas collection device, and an extract is obtained in the separation kettle, which is rosin resin acid; the carrying agent is at least one of n-butanol, n-propanol, ethanol, methanol, and acetone.

2. The method for preparing a rosin resin acid according to claim 1, wherein: The mass ratio of the rosin to the carrying agent is 1:5 to 1:

50.

3. A method for preparing a rosin resin acid according to claim 1 or 2, characterized in that: The molar fraction of the carrying agent in CO2 is 5% to 35%.

4. The method for preparing a rosin resin acid according to claim 1, wherein: In the extraction kettle, the pressure is 10 MPa to 45 MPa, and the temperature is 313.15 K to 348.15 K.

5. The method for preparing a rosin resin acid according to claim 3, wherein: The pressure holding time is 30min to 80min.

Images