CN110818762B - Residual oil treatment method for recovering sterol and refining sylvite - Google Patents
Residual oil treatment method for recovering sterol and refining sylvite Download PDFInfo
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- CN110818762B CN110818762B CN201911137630.2A CN201911137630A CN110818762B CN 110818762 B CN110818762 B CN 110818762B CN 201911137630 A CN201911137630 A CN 201911137630A CN 110818762 B CN110818762 B CN 110818762B
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- sterol
- residual oil
- water
- methanol
- sylvite
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- 229930182558 Sterol Natural products 0.000 title claims abstract description 79
- 235000003702 sterols Nutrition 0.000 title claims abstract description 79
- 150000003432 sterols Chemical class 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 33
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 title claims abstract description 31
- 239000001103 potassium chloride Substances 0.000 title claims abstract description 31
- 235000011164 potassium chloride Nutrition 0.000 title claims abstract description 31
- 238000007670 refining Methods 0.000 title claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 147
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 82
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 69
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000000926 separation method Methods 0.000 claims abstract description 52
- 238000005406 washing Methods 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 17
- 230000008025 crystallization Effects 0.000 claims abstract description 17
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 14
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 230000008020 evaporation Effects 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 27
- 125000004185 ester group Chemical group 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 230000020477 pH reduction Effects 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 abstract description 21
- 125000005456 glyceride group Chemical group 0.000 abstract description 12
- 239000007787 solid Substances 0.000 abstract description 12
- -1 sterol esters Chemical class 0.000 abstract description 12
- 238000000746 purification Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000010364 biochemical engineering Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 150000002148 esters Chemical group 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 94
- 235000019198 oils Nutrition 0.000 description 94
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 22
- 229910052939 potassium sulfate Inorganic materials 0.000 description 22
- 235000011151 potassium sulphates Nutrition 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- 238000011084 recovery Methods 0.000 description 20
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 229930003427 Vitamin E Natural products 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 4
- 229940046009 vitamin E Drugs 0.000 description 4
- 235000019165 vitamin E Nutrition 0.000 description 4
- 239000011709 vitamin E Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000019482 Palm oil Nutrition 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Abstract
The invention provides a residual oil treatment method for recovering sterol and refining sylvite, which relates to the field of biochemical engineering and comprises the following steps of three-step reaction in the early stage and separation and purification in the later stage: in the first step of the invention, potassium hydroxide and methanol are heated and refluxed to react to obtain a mixed solution; secondly, mixing residual oil and the mixed solution for transesterification; thirdly, acidifying the product of the ester exchange reaction, and then standing and separating to obtain an upper oil phase and a lower water phase; the later separation and purification steps mainly adopt the means of water washing, evaporation separation, cold separation and crystallization, filtration and refining. The three-step reaction of the invention can convert sterol esters and glycerides in the residual oil into free sterols, glycerol and fatty acid methyl esters; the subsequent refining and separating step can recover solid sylvite, refined sterol, glycerin and methanol with high practicability, greatly reduce water treatment and salt discharge pollution, and have the characteristics of high sterol yield, environmental protection, no pollution and high comprehensive benefit.
Description
Technical Field
The invention relates to the technical field of biochemical engineering, in particular to a residual oil treatment method for recovering sterol and refining sylvite.
Background
During the production and refining of food oils such as soybean oil, rapeseed oil, peanut oil, sunflower oil, palm oil, etc., a large amount of deodorized distillates, so-called vegetable oil leftovers, are produced. In fact, the deodorized distillate also contains a large amount of useful components, such as natural vitamin E, sterols and other very valuable products, which can be further refined from the deodorized distillate. At present, most of the domestic and foreign treatment processes for deodorized distillates are as follows: firstly, carrying out sulfuric acid catalysis and alkali catalysis secondary alcoholization on the deodorized distillate, filtering and separating out crude sterol, carrying out molecular distillation on the filtrate to obtain vitamin E oil and fatty acid methyl ester, wherein the residue is residual oil.
Residual oil after vitamin E extraction generally accounts for 10-20% of the raw oil, and the residual oil still contains a small part of useful components, wherein the content of the contained sterol ester reaches about 10-11% of the residual oil, and the content of the glyceride reaches about 2-3% of the residual oil; at present, most of the residual oil is discharged as waste residue, which causes great pollution to the environment. Sodium hydroxide and sodium carbonate are generally adopted as catalysts in the existing residual oil treatment method, sodium salt generated in the process flow has no practical value, and the phenomenon of emission pollution still exists due to the imperfect treatment method. Therefore, a new method which can comprehensively recover various useful substances in the residual oil and is beneficial to environmental protection needs to be developed.
Disclosure of Invention
In view of the above, the present invention aims to provide a residual oil treatment method for recovering sterols and refining sylvite, which has the characteristics of less pollution, simple operation and high sterol yield, and can recover refined sylvite and glycerol with high practicability in the treatment process.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a residual oil treatment method for recovering sterol and refining sylvite, which comprises the following steps:
heating potassium hydroxide and methanol for reflux, and reacting to obtain a mixed solution;
mixing residual oil and the mixed solution for transesterification reaction to obtain a transesterification product;
acidifying the ester exchange product, and then standing and separating to obtain an upper oil phase and a lower water phase;
washing the upper oil phase with water, standing and separating to obtain a water washing liquid and a second upper oil phase;
combining the lower-layer water phase and the water washing liquid, and then carrying out evaporation separation to obtain water, methanol, crude potassium salt and glycerol respectively; washing and drying the crude sylvite to obtain refined sylvite;
and (3) carrying out cold crystallization, filtration and refining treatment on the second upper oil phase in sequence to obtain refined sterol.
Preferably, the heating reflux temperature of the potassium hydroxide and the methanol is 60-75 ℃, and the time is 4-8 h.
Preferably, the temperature of the ester exchange reaction is 75-85 ℃, and the time is 3-6 h.
Preferably, the mass ratio of the potassium hydroxide to the methanol to the residual oil is 9-17: 120-180: 160-200.
Preferably, the acid for acidification is concentrated sulfuric acid with the mass concentration of 98%, the standing and separating time after acidification is 1h, and the pH value of the upper oil phase is 6-6.8.
Preferably, the temperature of the water for water washing treatment is 80-90 ℃, the time for standing separation after water washing treatment is 2-3 h, and the pH value of the second upper oil phase is 7.
Preferably, the evaporation separation is performed by using a double-effect evaporator, specifically: the heating temperature of the separated methanol is 80-90 ℃, the heating temperature of the separated water is 100-110 ℃, and the remainder is glycerol and crude sylvite.
Preferably, the temperature of the cold separation crystallization is 5-10 ℃, and the filtration is plate-and-frame filtration.
Preferably, the refining treatment is: and rinsing the filtered crude sterol 2-4 times by using absolute ethyl alcohol.
Has the advantages that:
the invention provides a residual oil treatment method for recovering sterol and refining sylvite, which mainly comprises three steps of reaction in the early stage and separation and purification in the later stage:
in the first step of the invention, potassium hydroxide and methanol are heated and refluxed to react to obtain a mixed solution; secondly, mixing residual oil and the mixed solution for transesterification; and thirdly, acidifying the product of the ester exchange reaction, and standing and separating to obtain an upper oil phase and a lower water phase. The three-step reaction in the early stage of the invention adopts methanol as a solvent, generates potassium methoxide as an alkali catalyst, and heats the residual oil for ester exchange reaction, so that sterol ester and glyceride in the residual oil are converted into free sterol, glycerol and fatty acid methyl ester.
The later separation and purification steps of the invention mainly adopt the means of water washing, evaporation separation, cold separation and crystallization, filtration and refining. The separation and purification operation is simple and feasible, the crude sylvite, the refined sterol, the glycerol and the methanol with high practicability can be recovered, the water treatment and the salt discharge pollution are greatly reduced, and the method has the characteristic of high sterol yield; meanwhile, the refined crude sylvite can be used in the field of fertilizers, so that the value gain is realized.
The invention realizes the environmental protection and no pollution of the whole flow of the residual oil treatment method and has high comprehensive benefit.
The results of the examples show that after 1500kg of residual oil (sterol ester content 12%, glyceride content 2.5%) is treated by the method provided by the invention, 220kg of refined sterol and 53kg of glycerol (content 80%) can be obtained, according to the input amount of potassium hydroxide, the recovery rate of the refined potassium sulfate can reach more than 200kg, and the recovery rates of the refined sterol and the potassium sulfate are both more than 95%.
Detailed Description
The invention provides a residual oil treatment method for recovering sterol and refining sylvite, which comprises the following steps:
heating potassium hydroxide and methanol for reflux, and reacting to obtain a mixed solution;
mixing residual oil and the mixed solution for transesterification reaction to obtain a transesterification product;
acidifying the ester exchange product, and then standing and separating to obtain an upper oil phase and a lower water phase;
washing the upper oil phase with water, standing and separating to obtain a water washing liquid and a second upper oil phase;
combining the lower-layer water phase and the water washing liquid, and then carrying out evaporation separation to obtain water, methanol, crude potassium salt and glycerol respectively; washing and drying the crude sylvite to obtain refined sylvite;
and (3) carrying out cold crystallization, filtration and refining treatment on the second upper oil phase in sequence to obtain refined sterol.
The invention heats potassium hydroxide and methanol for reflux, and obtains mixed solution after reaction. In the present invention, the methanol is preferably anhydrous methanol, the purity of which is preferably > 99.5%; in the invention, the heating reflux temperature of the potassium hydroxide and the methanol is preferably 60-75 ℃, more preferably 68 ℃, and the time is preferably 4-8 h, more preferably 5-7 h, and further preferably 6 h. In the invention, potassium hydroxide solid and methanol are heated and refluxed to react, so that potassium methoxide is generated from potassium hydroxide and dissolved in methanol, and the obtained mixed solution can be used as a solvent and a catalyst for transesterification reaction, and the generated mixed solution is preferably kept at 50 ℃. The source of the potassium hydroxide and the anhydrous methanol is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used.
After the mixed solution is obtained, the residual oil and the mixed solution are mixed for ester exchange reaction to obtain an ester exchange product. In the present invention, the residual oil is preferably a residual oil produced after vitamin E is extracted from a deodorized distillate of a food oil such as soybean oil, rapeseed oil, peanut oil, sunflower seed oil, palm oil, or the like; the mass fraction of sterol ester in the residual oil raw material is preferably 10-15%, the mass fraction of glyceride is preferably 2-3%, and the mass fraction of water is preferably less than 1%. In the invention, the mass ratio of the potassium hydroxide to the methanol to the residual oil is preferably 9-17: 120-180: 160-200, more preferably 12-15: 140-160: 170-190, and further preferably 13:150: 180. In the invention, the temperature of the ester exchange reaction is preferably 75-85 ℃, more preferably 80 ℃, and the time is preferably 3-6 h, more preferably 4-5 h, and further preferably 4.5 h. In the invention, methanol is used as a solvent, potassium methoxide is generated to be used as an alkali catalyst, and residual oil is heated to carry out transesterification reaction, so that sterol ester and glyceride in the residual oil are converted into free sterol, glycerol and fatty acid methyl ester.
In the invention, the container used for the heating reflux reaction of potassium hydroxide and methanol and the ester exchange reaction after adding residual oil is preferably an autoclave, methanol reflux is kept in the heating process, the residual oil is directly added into the autoclave for the ester exchange reaction after the heating reflux of potassium hydroxide and methanol is finished, and the pressure of the autoclave is preferably 5-7 MPa, more preferably 6MPa when the ester exchange reaction is carried out.
After the ester exchange product is obtained, the ester exchange product is acidified and then is kept stand and separated to obtain an upper oil phase and a lower water phase. In the invention, the acid for acidification treatment is preferably concentrated sulfuric acid with the mass concentration of 98%, the concentrated sulfuric acid is preferably added in a stirring manner, the stirring speed is not required, and the purpose of acidification treatment is to neutralize alkali in the reaction solution; the temperature of the acidification treatment is preferably 70-90 ℃, and the time is preferably 0.5 h. In the invention, the time of standing and separating after the acidification treatment is preferably 1h, and a lower water phase and an upper oil phase dissolved with potassium sulfate are obtained after standing; in the invention, the pH value of the lower water phase is preferably 6-6.8, and more preferably 6.5.
After the upper oil phase is obtained, the upper oil phase is subjected to water washing treatment and then is subjected to standing separation to obtain a water washing liquid and a second upper oil phase. In the invention, the temperature of the water for water washing treatment is preferably 80-90 ℃, more preferably 85 ℃, and the time for standing and separating after the water washing treatment is preferably 2-3 h, more preferably 2.5 h. In the invention, preferably, the raw materials are subjected to 1-4 times of water washing treatment and then are subjected to standing separation, and in the specific embodiment of the invention, the water consumption for each time is preferably one third of the weight of the adopted anhydrous methanol; the pH of the resulting second upper oil phase was adjusted to 7.
After a second upper oil phase is obtained, the second upper oil phase is sequentially subjected to cold crystallization, filtration and refining treatment to obtain refined sterol. In the invention, a cold separation kettle is preferably adopted for cold separation crystallization, and the temperature of the cold separation crystallization is preferably 5-10 ℃, and more preferably 6-8 ℃; after cold separation crystallization is finished, filtering the crystallization liquid, preferably performing plate-and-frame filtration by using a filtering method, and obtaining crude sterol by using the plate-and-frame filtration; in the present invention, the purification treatment is preferably: and rinsing the filtered crude sterol for 2-4 times by using absolute ethyl alcohol to obtain refined sterol.
After water washing liquid is obtained, the lower-layer water phase and the water washing liquid are combined and then are subjected to evaporation separation to respectively obtain water, methanol, crude potassium salt and glycerol; and washing and drying the crude potassium salt to obtain the refined potassium salt. In the invention, the evaporation treatment preferably adopts a double-effect evaporator, and the double-effect evaporator is more energy-saving and environment-friendly. In the present invention, when the evaporation separation is performed using a double-effect evaporator, it is particularly preferable that: the heating temperature of the separated methanol is 80-90 ℃, the heating temperature of the separated water is 100-110 ℃, and the remainder is glycerol and crude sylvite. In the specific embodiment of the invention, the lower-layer water phase and the washing liquid are combined and then directly heated, the heating rate of heating is controlled, the temperature is further raised to 100-110 ℃ after methanol is evaporated, and water is separated; then respectively obtaining methanol and water by condensation; the remainder was glycerol with a higher boiling point and crude potassium salt.
After the evaporation separation is finished, the crude sylvite is washed and dried to obtain refined sylvite; in the invention, the washing detergent is preferably absolute ethyl alcohol, and the washing times are preferably 2-5 times.
The method for treating residual oil to recover sterols and refine potassium salt according to the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A residual oil treatment method for recovering sterol and refining sylvite comprises the following steps:
(1) heating 132kg of potassium hydroxide and 1500kg of anhydrous methanol (with the content of 99.9%) in a 5-ton reaction kettle to 65 ℃, refluxing for 4 hours to react to obtain a mixed solution, and cooling to 50 ℃;
(2) adding 1800kg of residual oil (the content of sterol ester is 12%, and the content of glyceride is 2.5%) into the mixed solution, heating to 80 ℃, and carrying out transesterification reaction for 4h to obtain a transesterification product;
(3) acidifying the ester exchange product, adding 160kg of concentrated sulfuric acid with the concentration of 98% while stirring, standing for 1h, and separating to obtain an upper oil phase and a lower water phase;
(4) washing the upper oil phase with 80 deg.C hot water for 3 times (500 kg each time, standing for separation to obtain water washing solution and second upper oil phase) to obtain oil phase with pH of 7;
(5) combining the lower-layer water phase in the step (3) and the water washing liquid in the step (4), putting the mixture into a double-effect evaporator for separation, and respectively recovering 266kg (with the content of 75%) of methanol, water, crude potassium sulfate solid and 53kg (with the content of 80%) of glycerol;
(6) transferring the second upper oil phase obtained in the step (4) into a cold separation kettle, performing cold separation and crystallization to 10 ℃, and filtering and pressing by using a plate frame to obtain 312kg of crude sterol (the content is 69%, and the cold separation recovery rate of the crude sterol is 99%);
(7) rinsing the crude sterol with 1000kg of absolute ethanol for 3 times to obtain 220.8kg of refined sterol (the content is 96%, and the rinsing recovery rate of the refined sterol is 98%);
(8) washing the crude potassium sulfate solid in the step (5) for 3 times by using anhydrous methanol, and drying to obtain 202kg of refined potassium sulfate (the content is 96%, and the recovery rate of the potassium salt is 95.5%).
Example 2
A residual oil treatment method for recovering sterol and refining sylvite comprises the following steps:
(1) heating 110kg of potassium hydroxide and 1500kg of anhydrous methanol (with the content of 99.9%) in a 5-ton reaction kettle to 65 ℃, refluxing for 4 hours to react to obtain a mixed solution, and cooling to 50 ℃;
(2) adding 1800kg of residual oil (the content of sterol ester is 12%, and the content of glyceride is 2.5%) into the mixed solution, heating to 85 ℃, and carrying out ester exchange reaction for 4 hours to obtain an ester exchange product;
(3) acidifying the ester exchange product, adding 160kg of 98% concentrated sulfuric acid under stirring, standing for 1h, and separating to obtain an upper oil phase and a lower water phase;
(4) washing the upper oil phase with 85 deg.C hot water for 3 times (500 kg each time, standing for separation to obtain water washing solution and second upper oil phase) to obtain oil phase with pH of 7;
(5) combining the lower-layer water phase in the step (3) and the water washing liquid in the step (4), putting the mixture into a double-effect evaporator for separation, and respectively recovering 231kg (with the content of 75%) of methanol, water, crude potassium sulfate solid and 53kg (with the content of 80%) of glycerol;
(6) transferring the second upper oil phase obtained in the step (4) into a cold separation kettle, performing cold separation and crystallization to 10 ℃, and filtering and pressing by using a plate frame to obtain 284kg of crude sterol (the content is 69%, and the cold separation recovery rate of the crude sterol is 99%);
(7) rinsing the crude sterol with 1000kg of absolute ethanol for 3 times to obtain 203kg of refined sterol (the content is 96%, and the rinsing recovery rate of the refined sterol is 98%);
(8) and (3) washing the crude potassium sulfate solid in the step (5) for 3 times by using anhydrous methanol, and drying to obtain 169kg of refined potassium sulfate (the content is 96%, and the potassium salt recovery rate is 95.5%).
Example 3
A residual oil treatment method for recovering sterol and refining sylvite comprises the following steps:
(1) heating 90kg of potassium hydroxide and 1500kg of anhydrous methanol (with the content of 99.9%) in a 5-ton reaction kettle to 70 ℃, refluxing for 5 hours to react to obtain a mixed solution, and cooling to 50 ℃;
(2) adding 1800kg of residual oil (the sterol ester content is 12% and the glyceride content is 2.5%) into the mixed solution, heating to 85 ℃, and carrying out transesterification reaction for 3.5h to obtain a transesterification product;
(3) acidifying the ester exchange product, adding 160kg of concentrated sulfuric acid with the concentration of 98% while stirring, standing for 1h, and separating to obtain an upper oil phase and a lower water phase;
(4) washing the upper oil phase with 80 deg.C hot water for 3 times (500 kg each time, standing for separation to obtain water washing solution and second upper oil phase) to obtain oil phase with pH of 7;
(5) combining the lower-layer water phase in the step (3) and the water washing liquid in the step (4), putting the mixture into a double-effect evaporator for separation, and respectively recovering 183kg (with the content of 75%) of methanol, water, crude potassium sulfate solid and 53kg (with the content of 80%) of glycerol;
(6) transferring the second upper oil phase obtained in the step (4) into a cold separation kettle, performing cold separation and crystallization to 10 ℃, and filtering and pressing 255kg of crude sterol by using a plate frame (the content is 69%, and the cold separation recovery rate of the crude sterol is 99%);
(7) rinsing the crude sterol with 1000kg of absolute ethanol for 3 times to obtain 180kg of refined sterol (the content is 96%, and the rinsing recovery rate of the refined sterol is 98%);
(8) and (3) washing the crude potassium sulfate solid in the step (5) for 3 times by using anhydrous methanol, and drying to obtain 138kg of refined potassium sulfate (the content is 96%, and the recovery rate of the potassium salt is 95.5%).
Example 4
A residual oil treatment method for recovering sterol and refining sylvite comprises the following steps:
(1) heating 150kg of potassium hydroxide and 1500kg of anhydrous methanol (with the content of 99.9%) in a 5-ton reaction kettle to 75 ℃, refluxing for 4 hours to react to obtain a mixed solution, and cooling to 50 ℃;
(2) adding 1800kg of residual oil (the content of sterol ester is 12%, and the content of glyceride is 2.5%) into the mixed solution, heating to 78 ℃, and carrying out ester exchange reaction for 6h to obtain an ester exchange product;
(3) acidifying the ester exchange product, adding 160kg of concentrated sulfuric acid with the concentration of 98% while stirring, standing for 1h, and separating to obtain an upper oil phase and a lower water phase;
(4) washing the upper oil phase with 82 deg.C hot water for 4 times (500 kg each time, standing for separation to obtain water washing solution and second upper oil phase) to obtain oil phase with pH of 7;
(5) combining the lower-layer water phase in the step (3) and the water washing liquid in the step (4), putting the mixture into a double-effect evaporator for separation, and respectively recovering 304kg (the content is 75%) of methanol, water, crude potassium sulfate solid and 53kg (the content is 80%) of glycerol;
(6) transferring the second upper oil phase obtained in the step (4) into a cold separation kettle, performing cold separation and crystallization to 10 ℃, and filtering and pressing by using a plate frame to obtain 312kg of crude sterol (the content is 69%, and the cold separation recovery rate of the crude sterol is 99%);
(7) rinsing the crude sterol with 1000kg of absolute ethanol for 3 times to obtain 220.8kg of refined sterol (the content is 96%, and the rinsing recovery rate of the refined sterol is 98%);
(8) and (3) washing the crude potassium sulfate solid in the step (5) for 3 times by using anhydrous methanol, and drying to obtain 231kg of refined potassium sulfate (the content is 96%, and the potassium salt recovery rate is 95.5%).
Example 5
A residual oil treatment method for recovering sterol and refining sylvite comprises the following steps:
(1) heating 160kg of potassium hydroxide and 1500kg of anhydrous methanol (with the content of 99.9%) in a 5-ton reaction kettle to 70 ℃, refluxing for 6 hours to react to obtain a mixed solution, and cooling to 50 ℃;
(2) adding 1800kg of residual oil (the content of sterol ester is 12%, and the content of glyceride is 2.5%) into the mixed solution, heating to 82 ℃, and carrying out ester exchange reaction for 5 hours to obtain an ester exchange product;
(3) acidifying the ester exchange product, adding 160kg of concentrated sulfuric acid with the concentration of 98% while stirring, standing for 1h, and separating to obtain an upper oil phase and a lower water phase;
(4) washing the upper oil phase with 80 deg.C hot water for 3 times (500 kg each time, standing for separation to obtain water washing solution and second upper oil phase) with pH of 7;
(5) combining the lower-layer water phase in the step (3) and the water washing liquid in the step (4), putting the mixture into a double-effect evaporator for separation, and respectively recovering 325kg (the content is 75%) of methanol, water, crude potassium sulfate solid and 53kg (the content is 80%) of glycerol;
(6) transferring the second upper oil phase obtained in the step (4) into a cold separation kettle, performing cold separation and crystallization to 10 ℃, and filtering and pressing by using a plate frame to obtain 312kg of crude sterol (the content is 69%, and the cold separation recovery rate of the crude sterol is 99%);
(7) rinsing the crude sterol with 1000kg of anhydrous ethanol for 3 times to obtain 220.8kg of refined sterol (the content is 96%, the rinsing recovery rate of the refined sterol is 98%);
(8) and (3) washing the crude potassium sulfate solid in the step (5) for 3 times by using anhydrous methanol, and drying to obtain 247kg of refined potassium sulfate (the content is 96%, and the recovery rate of the potassium salt is 95.5%).
According to the invention, the recovery data of refined sterol, refined potassium sulfate and glycerol in the residual oil treatment method for recovering sterol and refining sylvite provided in the embodiment 1-5 are analyzed and summarized, and the specific results are shown in table 1.
TABLE 1 refined sterol, potassium sulfate and glycerol recovery data for the residuum treatment processes of examples 1-5
As can be seen from the examples and the data in Table 1, the residual oil treatment method for recovering sterol and refining sylvite provided in the examples 1-5 of the invention has the characteristics of less pollution, simple operation and high sterol yield, and potassium sulfate and glycerol with higher practical values can be recovered in the treatment process; after the residual oil (the content of sterol ester is 10-15%, the content of glyceride is 2-3%, and the water content is less than 1%) is treated by the residual oil method provided by the invention, the recovery rate of the obtained refined sterol and potassium sulfate is more than 95%, and the comprehensive benefit is very good.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A residual oil treatment method for recovering sterol and refining sylvite is characterized by comprising the following steps:
heating potassium hydroxide and methanol for reflux, and reacting to obtain a mixed solution;
mixing residual oil and the mixed solution for transesterification reaction to obtain a transesterification product;
acidifying the ester exchange product, and then standing and separating to obtain an upper oil phase and a lower water phase;
washing the upper oil phase with water, standing and separating to obtain a water washing liquid and a second upper oil phase;
combining the lower-layer water phase and the water washing liquid, and then carrying out evaporation separation to obtain water, methanol, crude potassium salt and glycerol respectively; washing and drying the crude sylvite to obtain refined sylvite;
sequentially carrying out cold crystallization, filtration and refining treatment on the second upper oil phase to obtain refined sterol; the refining treatment comprises the following steps: rinsing the filtered crude sterol 2-4 times by using absolute ethyl alcohol;
the temperature of the ester exchange reaction is 75-85 ℃, and the time is 3-6 h;
the acid for acidification is concentrated sulfuric acid with the mass concentration of 98%, the standing separation time after acidification is 1h, and the pH value of the upper oil phase is 6-6.8;
the temperature of the water for water washing treatment is 80-90 ℃, the time for standing separation after water washing treatment is 2-3 h, and the pH value of the second upper oil phase is 7;
the evaporation separation is carried out by adopting a double-effect evaporator, and specifically comprises the following steps: the heating temperature of the separated methanol is 80-90 ℃, the heating temperature of the separated water is 100-110 ℃, and the remainder is glycerol and crude sylvite.
2. The method of claim 1, wherein the heating reflux temperature of potassium hydroxide and methanol is 60 ℃ to 75 ℃ for 4 to 8 hours.
3. A residual oil treatment method according to claim 1 or 2, characterized in that the mass ratio of potassium hydroxide, methanol and residual oil is 9-17: 120-180: 160-200.
4. A residual oil treatment method according to claim 1, characterized in that the temperature of the cold crystallization is 5-10 ℃, and the filtration is plate-and-frame filtration.
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| CN111777655B (en) * | 2020-07-27 | 2021-06-25 | 福建省格兰尼生物工程股份有限公司 | Method for extracting wood sterol from tall oil pitch |
| CN111718390B (en) * | 2020-07-28 | 2023-06-16 | 福建省格兰尼生物工程股份有限公司 | Sterol cold precipitation formula liquid and application thereof |
| CN114891055A (en) * | 2022-04-13 | 2022-08-12 | 福建省格兰尼生物工程股份有限公司 | Method for extracting sterol from plant residual oil by chemical and biological methods |
| CN115074411A (en) * | 2022-04-13 | 2022-09-20 | 福建省格兰尼生物工程股份有限公司 | Biological enzyme treatment method for transesterification products in plant residual oil recycling |
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