CN105524713B - Industrialized method for removing rubber from rubber tree seed oil - Google Patents

Industrialized method for removing rubber from rubber tree seed oil Download PDF

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CN105524713B
CN105524713B CN201610075658.8A CN201610075658A CN105524713B CN 105524713 B CN105524713 B CN 105524713B CN 201610075658 A CN201610075658 A CN 201610075658A CN 105524713 B CN105524713 B CN 105524713B
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rubber
seed oil
tree seed
rubber tree
oil
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CN105524713A (en
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朱义鑫
王云
张娜娜
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XISHUANGBANNA HUAKUN BIOTECHNOLOGY CO Ltd
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XISHUANGBANNA HUAKUN BIOTECHNOLOGY CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/12—Refining fats or fatty oils by distillation

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

the invention relates to an industrialized method for removing rubber from rubber tree seed oil, belonging to the technical field of vegetable oil processing. Firstly, according to the content of natural rubber in the rubber tree seed oil, adding active carbon which is 0.5-2.0 times of the weight of the natural rubber, heating to 90-120 ℃, and stirring for 14-16 minutes; then adding activated clay with the mass being 3-6% of the mass of the rubber tree seed oil, keeping the temperature at 90-120 ℃, and stirring for 14-16 minutes; then filtering the material to filter out active carbon and active clay, wherein the oil temperature during filtering is kept above 90 ℃; and finally, heating the rubber tree seed oil to 200-260 ℃ in a sealed container under the absolute pressure of less than 500Pa, and carrying out thermal decomposition of the natural rubber and distillation and volatilization of the decomposition products to obtain the rubber tree seed oil. The method has the advantages of good rubber removal effect, thorough removal, no introduction of new solvent, high production efficiency and realization of large-scale production.

Description

Industrialized method for removing rubber from rubber tree seed oil
Technical Field
The invention belongs to the technical field of vegetable oil processing, and particularly relates to an industrialized method for removing rubber from rubber tree seed oil.
Background
The rubber tree seed oil is vegetable oil extracted from rubber tree seeds, and belongs to precious tropical woody oil. The fatty acid of rubber tree seed oil mainly contains palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid, the degree of unsaturation (total unsaturated fatty acid) is up to 83%, and especially contains 20% of linolenic acid. Research of a plurality of research institutions at home and abroad shows that the rubber tree seed oil not only has high nutritive value, but also has the health care effects of preventing cardiovascular diseases and promoting regression of atherosclerosis, and is an oil material with practical value and health care effect.
The rubber seed kernel contains a small amount of natural rubber (polyisoprene), and when oil is extracted, part of the natural rubber is dissolved in rubber tree seed oil. Research shows that the natural rubber in the rubber tree seed oil accounts for 0.1-0.4%, and the natural rubber is different according to different varieties of rubber trees and different oil preparation methods. Natural rubber is not a conventional ingredient in edible fats and oils and must be removed.
The methods for removing rubber from rubber tree seed oil disclosed in the literature and patents are roughly classified into specific methods and non-specific methods. The specific method can remove the natural rubber in a targeted manner, and has good removal effect and thorough removal. The method for specifically removing rubber in rubber tree seed oil mainly comprises a solvent precipitation method and a membrane filtration method.
The solvent precipitation method is described in patent number ZL200910094034.0 "method and device for removing rubber from rubber tree seed oil", and comprises mixing acetone as main solvent into rubber tree seed oil, precipitating polyisoprene, and distilling to remove acetone solvent to obtain rubber tree seed oil. However, this approach has two major disadvantages: firstly, an organic solvent is introduced, so that solvent residues are generated; second, the removal of polyisoprene simultaneously removes the nutritional and health-promoting minor constituents of the rubber tree seed oil, such as phospholipids, sterols, vitamin E, and the like.
Membrane filtration method As described in "a method for removing rubber by high-efficiency membrane filtration of rubber seed oil (application No. CN 201410846892.7)", natural rubber is filtered by using a ceramic membrane according to the difference between the molecular weights of natural rubber and triglyceride. The advantages of membrane filtration are many, the processed product has good quality, but the equipment investment is large at one time, the filtration efficiency is low, and the membrane filtration is not suitable for large-scale continuous production.
The non-specific method is to remove the natural rubber non-specifically while degumming the grease. The nonspecific method has poor effect of removing the natural rubber, and the removal is not thorough. The reason for this is as follows:
1. The "glue" in the grease industry is also called "colloid", and refers to an unstable colloidal substance dispersed in grease, which can be deposited at the bottom of a container to become oil residue after long-term storage. The main chemical component of the colloid is phospholipid, which is an amphiphilic substance and is hydrophilic and lipophilic. The degumming principle is that the oil is added with water and stirred under the neutral (hydration degumming) or acidic (phosphoric acid or formic acid degumming) condition to make the hydrophilic group of phospholipid absorb water and expand to become hydrated phospholipid micelle. After the phospholipid is hydrated, it becomes more hydrophilic and more oleophobic, and cannot be stably dispersed in the oil, so that it is flocculated and precipitated.
2. Natural rubber, although also a sticky "gum", is a purely hydrocarbon (polyisoprene) strictly oleophilic molecule, free of any hydrophilic groups (oxygen and other atoms). Therefore, neither hydration degumming nor acidification degumming can ensure that the natural rubber molecules absorb water and precipitate.
Hydration degumming or acidification degumming is called nonspecific degumming because phospholipids can entrain some high molecular natural rubber during water swelling and flocculation precipitation. However, this entrainment is non-specific, non-selective, and incomplete. According to literature data, the following academic papers relate to techniques and processes for non-specific removal of rubber from rubber tree seed oil:
1. The refining research of rubber seed oil (author Wang Xiaoli, Jalin China grease journal, 2000, 25(4): 10-11) proposes to remove trace rubber in rubber seed oil by formic acid.
2. Research on the preparation and refining of rubber seed oil (authors: Heway, Liu Da Chuan, Zhang Xin, China oil & fat journal, 2005, 30(11): 65-67) considers that phosphoric acid can be used to remove rubber, and considers that the principle is as follows: the addition of phosphoric acid also oxidizes the rubber hydrocarbon double bonds of the highly dispersed phase to peroxide rubber. Under the action of heat, the oil shrinks to form aggregates which are separated from the oil. "the person skilled in the art is unsurpassed to this conclusion as regards the phosphoric acid believed in this paper to cause the rubber to oxidize bihydrocarbons to peroxidized rubbers. Since phosphoric acid is not recognized as a strong oxidizing agent, phosphoric acid cannot oxidize carbon-carbon double bonds.
3. In the rubber seed oil production process and practice (Gimbag, China journal of fat and oil 2006, 31(2): 12-14), formic acid is adopted to remove rubber, and the rubber removal method comprises the following steps: the method comprises the steps of removing rubber by formic acid, heating clear oil without phospholipid to 60-70 ℃, adding formic acid (food grade) with the weight of 0.1% of that of oil, reacting for 20-25 min, standing and precipitating, and washing for 2-3 times by adding water. "
4. In the research on the degumming and decoloring process of rubber seed oil (authors' Tantao, Huangtao, Suminghua, Proc. Wuhan Industrial academy, 2007, 26(2): 9-11), 4 methods are adopted for degumming (authors consider that the meaning of gum includes rubber and colloid), and the 4 methods are respectively as follows: hydration degumming; degumming by phosphoric acid; ③ degumming by freezing phosphoric acid; and fourthly, degumming by a two-step method of phosphoric acid and formic acid. The authors considered the process iv to be relatively efficient and the reason for the analysis was that the second degumming with formic acid was specific to the rubber.
5. Research and practice on refining of rubber seed oil (authors luo xian, zhuyin, which bond, lie linkai, journal of grain and oil processing, 2009(11): 46-49), authors did not specifically distinguish between degummed and degummed (phospholipids), and tried 4 methods: adding phosphoric acid and calcium carbonate for hydration; adding phosphoric acid and then adding formic acid for hydration; thirdly, adding phosphoric acid to hydrate independently; fourthly, directly hydrating without adding additives. Finally, a degumming method of adding phosphoric acid for hydration separately is adopted. The operation method and the process parameters are as follows: adjusting the oil temperature to 40 ℃, adding 85% edible-grade phosphoric acid, wherein the adding amount is 3 per mill of the oil weight, fully stirring and mixing, adjusting the temperature to 80 ℃, adding 8% of the same-temperature soft water under rapid stirring, adding water, slowly stirring, heating, adjusting the final temperature to about 85 ℃, continuing stirring for 30min after reaching the final temperature, stopping stirring, standing and settling for more than 6h, discharging oil residue, sewage and dirty oil, and performing vacuum dehydration on the hydrated oil.
6. In the research on rubber seed oil short-distance/molecular distillation process (author Li Lin, Li Gem, ceramic silver, grain and oil processing: electronic journal, 2015(9): 26-28), the idea of the author is the same as the research and practice of rubber seed oil refining, 4 methods are tried, and finally, the method for independently adding phosphoric acid for hydration and degumming is optimized.
in summary, the methods for removing rubber from rubber tree seed oil can be divided into specific removal methods and non-specific removal methods. The specific removing method has good rubber removing effect and thorough removal, but has the defects of introduction of chemical solvent or low production efficiency. The nonspecific rubber removal method can be combined with a degumming method in oil refining, no additional step is added, and the method is suitable for large-scale production, but has the problems of poor rubber removal effect and incomplete removal. Therefore, how to overcome the defects of the prior art is a problem which needs to be solved urgently in the technical field of vegetable oil processing at present.
Disclosure of Invention
Aiming at the problems of the existing rubber tree seed oil rubber removal method, the invention finds a method which has good rubber removal effect, thorough removal, no introduction of new solvent, high production efficiency and can realize large-scale production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
An industrialized method for removing rubber from rubber tree seed oil comprises the following steps:
Step (1), activated carbon specific adsorption: adding active carbon which is 0.5-2.0 times of the weight of the natural rubber according to the content of the natural rubber in the rubber tree seed oil, heating to 90-120 ℃, and stirring for 14-16 minutes;
Step (2), activated clay nonspecific adsorption: adding activated clay with the mass being 3-6% of that of the rubber tree seed oil into the material stirred in the step (1), keeping the temperature at 90-120 ℃, and stirring for 14-16 minutes;
Step (3), non-specific filtration: filtering the material stirred in the step (2) to remove active carbon and active clay, wherein the oil temperature during filtering is kept above 90 ℃;
And (4) thermally decomposing residual natural rubber: heating the rubber tree seed oil to 200-260 ℃ in a sealed container with the absolute pressure of less than 500Pa, maintaining the temperature for more than 5min, and performing thermal decomposition of the natural rubber and distillation volatilization of the decomposition products.
Wherein the decomposition products are mainly isoprene tetramers and trimers of 20 carbons and 15 carbons.
In the present invention, thermal decomposition and distillative volatilization of the decomposition product are carried out simultaneously.
Further, it is preferable that the mass of the activated carbon added in the step (1) is 0.8 to 1.2 times the mass of the natural rubber in the rubber tree seed oil.
Further, in order to reduce oxidation of fats and oils, it is preferable that the stirring in the steps (1) and (2) is carried out in a sealed tank having an absolute pressure of less than 20 kPa.
Further, it is preferable that the added amount of activated clay in the step (2) is 4 to 5% by mass based on the mass of the rubber tree seed oil.
further, it is preferable that the filtration in the step (3) is performed by a leaf filter or a plate and frame filter.
Further, it is preferable that the sealed container in the step (4) is a sealed tank or a sealed packed tower.
Further, it is preferable that the heating temperature in the step (4) is 220-240 ℃.
Further, it is preferable that the absolute pressure in the container at the time of heating in the step (4) is less than 250 Pa.
further, in order to make the natural rubber decomposition products (isoprene tetramers and trimers) more volatile, it is preferable to introduce water vapor during the heating of the rubber tree seed oil in step (4), and the amount of water vapor passing through is not particularly limited as long as the generated air flow can conveniently carry the thermal decomposition products out of the container.
Scientific and technical principle of the invention
The invention simultaneously uses three principles of removing natural rubber:
1. One of the principles is as follows: specific adsorption of active carbon to natural rubber
The chemical composition of natural rubber is polyisoprene, which is a pure hydrocarbon and has strict hydrophobicity. The activated carbon is a simple substance of carbon, and the structure of the activated carbon is porous and loose tiny graphite crystals. The graphite crystal is a sheet structure consisting of six honeycomb carbon rings, and carbon-carbon double bonds (the carbon-carbon double bonds comprise a sigma single bond and a conjugated pi bond) are combined among all carbon atoms. The active carbon has large surface area and strong adsorption capacity. But the activated carbon has certain selectivity on the adsorption substances, and the selectivity is that the adsorption on hydrophobic substances is larger than that on hydrophilic substances; the adsorption force for substances containing a relatively large number of carbon-carbon double bonds (including one sigma single bond and one pi bond) is greater than that for substances containing no carbon-carbon double bonds or having a small content of carbon-carbon double bonds.
Natural rubber is a strictly hydrophobic substance, does not contain oxygen atoms and other hydrophilic groups, and each monomer (5 carbon repeating units) thereof contains one carbon-carbon double bond (including one sigma single bond and one pi bond), so that the adsorption force of activated carbon to natural rubber is strong. The main component of the rubber tree seed oil is triglyceride, each triglyceride molecule contains 3 ester bonds, and the ester bonds belong to hydrophilic groups. Therefore, the adsorption capacity of the activated carbon on the triglyceride is weaker than that of the activated carbon on the natural rubber, and the natural rubber can be selectively adsorbed from the triglyceride, which belongs to specific adsorption.
2. And the second principle is nonspecific filtering of the natural rubber by the activated clay.
Activated clay belongs to activated silicate, and comprises calcium silicate, magnesium silicate, aluminum silicate, ferric silicate and the like. The activated clay also has strong adsorption capacity, but the activated clay is a hydrophilic substance, has stronger adsorption to the hydrophilic substance in the grease, and does not have the capacity of specifically adsorbing the natural rubber.
The removal of natural rubber by the activated clay is accomplished by filtration to form a filter cake. Natural rubber belongs to natural polymer materials. The molecular weight of natural rubber is 3-300 ten thousand daltons, the diameter of the molecule is in the range of 5-50nm, the molecular weight of the grease (triglyceride) is about 900 daltons, and the molecular diameter is less than 1 nm. Filtering after adding the activated clay into the grease to form a filter cake. The filter cake is a mesh-shaped structure consisting of activated clay fine particles, and the smaller the molecules (the lower the molecular weight and the smaller the diameter), the easier the filter cake can pass through the filter cake micropore mesh; the larger the molecule (high molecular weight, large diameter), the more easily it is intercepted by the filter cake microporous network. This is the principle of nonspecific filtering of natural rubber by activated clay.
The activated clay is added, so that the natural rubber is filtered in a non-specific manner, and the activated carbon also has the function of assisting the filtration and separation of the activated carbon from the rubber tree seed oil. Because the activated carbon can specifically adsorb natural rubber, after the rubber tree seed oil is added, a large number of natural rubber molecules can be adsorbed on the surface of the activated carbon particles to form an adhesion layer, and the adhesion layer becomes very viscous. If the traditional filtration mode (including plate-frame filtration and blade filtration) is adopted, the filter is easy to harden and block the filtration holes, so that the filtration is difficult. However, if activated clay is added, the non-viscous activated clay can wrap the viscous activated carbon to form a filter cake and play a role in assisting filtration because the amount of the activated clay is much larger than that of the activated carbon.
3. And thirdly, thermal decomposition and vacuum removal of the natural rubber.
Natural rubber (polyisoprene) is inferior in thermal stability to fats and oils (triglyceride), and when heated to a decomposition temperature, a high molecular carbon chain of natural rubber (polyisoprene) is broken to reduce the molecular weight. If the temperature is further increased, the polyisoprene carbon chain is broken more sharply, changing from a high molecular polymer to an oligomer of polyisoprene, or even forming isoprene monomers. High temperatures, although contributing to the decomposition of the natural rubber, also affect the quality of the grease, and therefore the temperature cannot be too high. According to the principle of chemical equilibrium, the forward progress of the chemical reaction is favored if the reaction product is removed from the reaction system. Since isoprene oligomers (tetramers or trimers) can volatilize from the rubber tree seed oil under high vacuum conditions, decomposition of natural rubber can be achieved and decomposition products can be removed under high vacuum conditions and at relatively low temperatures at which oils and fats remain stable. And introducing dry hot water vapor into the reaction system, wherein the water vapor can assist in carrying an isoprene oligomer (tetramer or trimer) reaction product, and the volatilization efficiency of the isoprene oligomer is improved. This is the principle of thermal decomposition and vacuum removal of natural rubber.
According to the experimental actual measurement (the measurement method is the measurement of the content of the natural rubber in the rubber tree seed oil of the enterprise standard Q/XSBNHK 0010-2015), in the invention, the activated carbon can specifically adsorb more than 80% of the natural rubber, and the activated clay can filter the residual natural rubber by about 20%. Residual less than 1% of natural rubber can be removed completely from the rubber tree seed oil by thermal decomposition and vacuum removal.
Compared with the prior art, the invention has the beneficial effects that:
the invention has good rubber removal effect, thorough removal, no introduction of new solvent, high production efficiency and realization of a large-scale method. Compared with other methods for removing rubber, the method is more suitable for large-scale continuous production, and the removal rate of the rubber is obviously higher than that of other methods proved by production practices; the invention has simple process flow, does not need to use organic chemical reagents as rubber removing agents and has high safety; the degumming process of the present invention can maintain the nutrient content of the rubber tree seed oil to a great extent.
Detailed Description
the present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available by purchase.
example 1
1) The crude oil of the rubber tree seed oil is squeezed at low temperature, and the content of natural rubber in the crude oil is measured to be 0.25 percent. Adding activated carbon 1 time of the weight of the natural rubber (namely 0.25 percent of the weight of the oil), heating to 120 ℃, and stirring for 15 minutes. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 15 kPa.
2) Adding activated clay 3.5 wt% of the oil, keeping the temperature at 120 ℃, and stirring for 15 minutes. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 15 kPa.
3) And a plate-frame filter is adopted to filter out the active carbon and the active clay, and the oil temperature is kept above 90 ℃ during filtering.
4) Heating rubber tree seed oil to 200 deg.C in a sealed container, maintaining for 5min under an absolute pressure of less than 250Pa, performing thermal decomposition of natural rubber, and introducing water vapor into the rubber tree seed oil to promote volatilization of rubber decomposition product. The rubber tree seed oil after the rubber removal has low viscosity, does not draw wires, does not turn black when heated to 280 ℃, and does not precipitate carbon fibers. The natural rubber content in the degummed crude oil is actually measured and is not detected.
Example 2
1) Squeezing crude oil of rubber tree seed oil at low temperature, wherein the natural rubber content is measured to be 0.25%. Adding activated carbon 1.2 times of the weight of the natural rubber (0.3% of the weight of the oil), heating to 110 ℃, and stirring for 14 minutes. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 20 kPa.
2) Adding activated clay 3 wt% of the oil, keeping the temperature at 90 ℃, and stirring for 14 minutes. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 20 kPa.
3) And a plate-frame filter is adopted to filter out the active carbon and the active clay, and the oil temperature is kept above 90 ℃ during filtering.
4) heating rubber tree seed oil to 200 deg.C in a sealed container, maintaining for 10min under an absolute pressure of less than 250Pa, performing thermal decomposition of natural rubber, and introducing water vapor into the rubber tree seed oil to promote volatilization of rubber decomposition product. The rubber tree seed oil after the rubber removal has low viscosity, does not draw wires, does not turn black when heated to 280 ℃, and does not precipitate carbon fibers. The natural rubber content in the degummed crude oil is actually measured and is not detected.
Example 3
1) The hot-pressed crude oil of rubber tree seed oil is actually measured, wherein the natural rubber content is 0.15%. Adding activated carbon 2 times the weight of the natural rubber (0.3% of the weight of the oil), heating to 120 ℃, and stirring for 16 minutes. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 15 kPa.
2) Adding activated clay 5 wt% of the oil, keeping the temperature at 120 ℃, and stirring for 16 minutes. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 15 kPa.
3) And a plate-frame filter is adopted to filter out the active carbon and the active clay, and the oil temperature is kept above 90 ℃ during filtering.
4) Heating rubber tree seed oil to 230 deg.C in a sealed container, maintaining for 12min under absolute pressure of less than 250Pa, performing thermal decomposition of natural rubber, and introducing water vapor into the rubber tree seed oil to promote volatilization of rubber decomposition product. The rubber tree seed oil after the rubber removal has low viscosity, does not draw wires, does not turn black when heated to 280 ℃, and does not precipitate carbon fibers. The natural rubber content in the degummed crude oil is actually measured and is not detected.
Example 4
1) the hot-pressed crude oil of rubber tree seed oil is actually measured, wherein the natural rubber content is 0.15%. Adding active carbon 0.8 times of the weight of natural rubber (0.2% of the weight of oil), heating to 100 deg.C, and stirring for 15 min. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 20 kPa.
2) Adding activated clay 4.5 wt% of the oil, keeping the temperature at 100 ℃, and stirring for 15 minutes. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 20 kPa.
3) And a plate-frame filter is adopted to filter out the active carbon and the active clay, and the oil temperature is kept above 90 ℃ during filtering.
4) Heating rubber tree seed oil to 230 deg.C in a sealed container, maintaining for 8min under absolute pressure of less than 250Pa, performing thermal decomposition of natural rubber, and introducing water vapor into the rubber tree seed oil to promote volatilization of rubber decomposition product. The rubber tree seed oil after the rubber removal has low viscosity, does not draw wires, does not turn black when heated to 280 ℃, and does not precipitate carbon fibers. The natural rubber content in the degummed crude oil is actually measured and is not detected.
Example 5
1) Crude oil of the seed oil of the rubber tree is leached, and the content of natural rubber in the crude oil is measured to be 0.4 percent. Adding active carbon 0.5 times of the natural rubber (0.2% of the oil), heating to 120 deg.C, and stirring for 15 min. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 15 kPa.
2) adding activated clay 4 wt% of the oil, keeping the temperature at 120 ℃, and stirring for 15 minutes. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 15 kPa.
3) And a plate-frame filter is adopted to filter out the active carbon and the active clay, and the oil temperature is kept above 90 ℃ during filtering.
4) Heating the rubber tree seed oil to 260 deg.C in a sealed container, maintaining for 10min under an absolute pressure of less than 250Pa, performing thermal decomposition of natural rubber, and introducing water vapor into the rubber tree seed oil to promote volatilization of rubber decomposition product. The rubber tree seed oil after the rubber removal has low viscosity, does not draw wires, does not turn black when heated to 280 ℃, and does not precipitate carbon fibers. The natural rubber content in the degummed crude oil is actually measured and is not detected.
Example 6
1) Crude oil of the seed oil of the rubber tree is leached, and the content of natural rubber in the crude oil is measured to be 0.4 percent. Adding activated carbon 1.5 times the weight of natural rubber (0.6% of oil weight), heating to 90 deg.C, and stirring for 15 min. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 20 kPa.
2) Adding activated clay 4 wt% of the oil, keeping the temperature at 100 ℃, and stirring for 15 minutes. The operation is carried out under negative pressure conditions inside the sealed tank, the absolute pressure inside the tank being less than 20 kPa.
3) And a plate-frame filter is adopted to filter out the active carbon and the active clay, and the oil temperature is kept above 90 ℃ during filtering.
4) Heating the rubber tree seed oil to 260 deg.C in a sealed container, maintaining for 10min under an absolute pressure of less than 250Pa, performing thermal decomposition of natural rubber, and introducing direct steam into the rubber tree seed oil to promote volatilization of rubber decomposition product. The rubber tree seed oil after the rubber removal has low viscosity, does not draw wires, does not turn black when heated to 280 ℃, and does not precipitate carbon fibers. The natural rubber content in the degummed crude oil is actually measured and is not detected.
Performance detection
The degumming rate of the rubber tree seed oil is only 50 percent ~ 60 percent in the actual production of formic acid degumming and acetone degumming (the result is shown in table 1), the degumming rate of the rubber tree seed oil can reach 99.99 percent, and the degumming result is not detected (less than 0.01 percent) by utilizing the enterprise standard Q/XSBNHK 0010 and 2015 determination of the natural rubber content in the rubber tree seed oil.
TABLE 1
Compared with other methods for removing rubber, the method is more suitable for large-scale continuous production, and the removal rate of the rubber is obviously higher than that of other methods proved by production practices; the invention has simple process flow, does not need to use organic chemical reagents as rubber removing agents and has high safety; the degumming process of the present invention can maintain the nutrient content of the rubber tree seed oil to a great extent.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

1. An industrialized method for removing rubber from rubber tree seed oil is characterized by comprising the following steps:
Step (1), activated carbon specific adsorption: adding active carbon which is 0.5-2.0 times of the weight of the natural rubber according to the content of the natural rubber in the rubber tree seed oil, heating to 90-120 ℃, and stirring for 14-16 minutes;
Step (2), activated clay nonspecific adsorption: adding activated clay with the mass being 3-6% of that of the rubber tree seed oil into the material stirred in the step (1), keeping the temperature at 90-120 ℃, and stirring for 14-16 minutes;
Step (3), non-specific filtration: filtering the material stirred in the step (2) to remove active carbon and active clay, wherein the oil temperature during filtering is kept above 90 ℃;
And (4) thermally decomposing residual natural rubber: heating the rubber tree seed oil to 200-260 ℃ in a sealed container with the absolute pressure of less than 500Pa, maintaining the temperature for more than 5min, and performing thermal decomposition of the natural rubber and distillation volatilization of decomposition products;
The filtration in the step (3) adopts a blade filter or a plate and frame filter; the sealed container in the step (4) is a sealed tank or a sealed packed tower.
2. The industrialized process for the de-rubberizing of rubber tree seed oil according to claim 1, wherein the mass of activated carbon added in step (1) is 0.8 to 1.2 times the mass of natural rubber in rubber tree seed oil.
3. the industrial process for the de-rubberizing of rubber tree seed oil of claim 1 wherein the agitation in steps (1) and (2) is in a sealed tank at an absolute pressure of less than 20 kPa.
4. the industrial process for the de-rubberizing of rubber tree seed oil according to claim 1, wherein the mass of activated clay added in step (2) is 4-5% of the mass of rubber tree seed oil.
5. The method for de-rubberizing of rubber tree seed oil in industrialization of claim 1, wherein the heating temperature in step (4) is 220-240 ℃.
6. the method of claim 1, wherein the absolute pressure in the container during heating is less than 250 Pa.
7. the method for de-rubberizing of rubber tree seed oil in claim 1, wherein water vapor is introduced during heating of rubber tree seed oil in step (4), and the generated air flow is used to carry thermal decomposition products.
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