CN111548860B - Process method for producing oleic acid by using plant waste oil - Google Patents
Process method for producing oleic acid by using plant waste oil Download PDFInfo
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- CN111548860B CN111548860B CN202010409604.7A CN202010409604A CN111548860B CN 111548860 B CN111548860 B CN 111548860B CN 202010409604 A CN202010409604 A CN 202010409604A CN 111548860 B CN111548860 B CN 111548860B
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N Oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000005642 Oleic acid Substances 0.000 title claims abstract description 30
- 239000010908 plant waste Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000005336 cracking Methods 0.000 claims abstract description 68
- 239000000126 substance Substances 0.000 claims abstract description 38
- 239000012535 impurity Substances 0.000 claims abstract description 29
- 238000000746 purification Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 137
- 239000000243 solution Substances 0.000 claims description 103
- 239000003921 oil Substances 0.000 claims description 84
- 235000019198 oils Nutrition 0.000 claims description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 80
- 239000008367 deionised water Substances 0.000 claims description 66
- 239000007788 liquid Substances 0.000 claims description 55
- 238000001914 filtration Methods 0.000 claims description 54
- 239000002253 acid Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 37
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 35
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 239000012295 chemical reaction liquid Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000002135 nanosheet Substances 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 24
- 239000002699 waste material Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 238000011068 load Methods 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- 239000004519 grease Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011858 nanopowder Substances 0.000 claims description 10
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- NOTVAPJNGZMVSD-UHFFFAOYSA-N Potassium oxide Chemical compound [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000007667 floating Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 8
- 239000008158 vegetable oil Substances 0.000 claims description 8
- 235000013311 vegetables Nutrition 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000002715 modification method Methods 0.000 claims description 5
- 230000001264 neutralization Effects 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000049 pigment Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 238000004945 emulsification Methods 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract description 2
- 230000002035 prolonged Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 36
- 235000021313 oleic acid Nutrition 0.000 description 25
- 239000010410 layer Substances 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008157 edible vegetable oil Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000003925 fat Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- OYHQOLUKZRVURQ-IXWMQOLASA-N Linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000008162 cooking oil Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000002209 hydrophobic Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229940037179 Potassium Ion Drugs 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003301 hydrolyzing Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/08—Refining
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/08—Refining
- C11C1/10—Refining by distillation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Abstract
The invention relates to the field of green environmental protection, in particular to a process method for producing oleic acid by using plant waste oil, which comprises the following steps: firstly, preprocessing; secondly, cracking; thirdly, post-treatment; and fourthly, purifying. The invention solves the problems that the freeze pressing method has low requirement on equipment, but has high labor intensity, low efficiency and can not be continuously operated; the surfactant method is also called as emulsification method, and the method has the problems of more waste water and lower separation purity. The pretreatment substance obtained by the method is pure, more than 95% of impurities and pigments are removed, guarantee is provided for subsequent cracking purification and reduction of equipment faults, and the service life of the equipment is prolonged.
Description
Technical Field
The invention relates to the field of environmental protection, in particular to a process method for producing oleic acid by using plant waste oil.
Background
The waste vegetable oil refers to a series of oil wastes which lose edible value and are generated in the deep processing process of edible natural vegetable oil and oil for human beings. Waste oil produced in the catering process is also called as catering waste oil. The fatty acid composition of the waste cooking oil is basically consistent with that of fresh edible oil, and the waste cooking oil mainly contains oleic acid and linoleic acid. The oil-containing soapstock produced in the food processing process is a byproduct produced in the refining of various vegetable oils, the production amount is 2-3% of the total oil production amount, and the composition and the properties of the oil-containing soapstock are determined by fatty acid in raw materials.
At present, the waste edible oil and fat in China are not reasonably utilized. In contrast, waste edible oils and fats have become an environmental pollutant and have impacted food safety. The waste edible oil is reasonably recycled, and the oil can replace petroleum resources to produce important oil chemical raw materials. The waste vegetable oil contains a large amount of stearic acid and oleic acid, and the oleic acid can be produced and processed by hydrolyzing and separating the waste edible oil. The following not enough exists in the processing procedure of present plant waste oil, and first, lack the preliminary treatment to waste oil, contain more impurity and pigment in the plant waste oil, direct processing uses influences equipment normal operating, and is great to equipment damage. Second, methods for purifying oleic acid include a freeze-squeezing method, a surfactant method, and the like. The freeze-pressing method has low requirements on equipment, but has high labor intensity and low efficiency and can not be continuously operated; the surfactant method is also called emulsification method, and the method has more waste water and lower separation purity.
Disclosure of Invention
Aiming at the problems, the invention provides a process method for producing oleic acid by using plant waste oil, which comprises the following steps:
first, pretreatment
Firstly, standing and settling vegetable waste oil for 10-12 hours, reserving upper-layer oil, and removing bottom impurities to obtain primary filtered oil; filtering the primary filtered oil to remove suspended and floating impurities to obtain secondary filtered oil;
adding a dilute acid solution into the second-stage filtered grease, stirring the mixture uniformly, then placing the mixture into a settling reaction kettle for settling for 1-2 hours, and filtering the mixture to obtain third-stage filtered grease;
pouring impurity-removing materials into the three-stage filtering grease, stirring for 2-3 h, and filtering again to obtain a pretreated substance;
second, cracking
Adding a cracking catalyst into the pretreated substance, starting stirring, and cracking to obtain a cracking product; wherein the cracking temperature is 200-230 ℃, the cracking pressure is 1.8-2.3 MPa, and the stirring speed is 200-500 rpm;
third, post-treatment
Adding a dilute acid solution into the cracked product again, heating to 60-70 ℃, and stirring for 2-5 hours to obtain a post-treated product;
the fourth step, purification
Purifying the post-treatment substance by adopting a 5-tower series rectification process to obtain oleic acid; wherein the temperature of the rectifying tower is 230-260 ℃, and the pressure of the top of the rectifying tower is 0.2-0.5 kPa.
Preferably, the dilute acid solution is a sulfuric acid aqueous solution with the concentration of 0.1 mol/L.
Preferably, the volume ratio of the secondary filtering grease to the dilute acid solution is 10-50: 1.
Preferably, the volume ratio of the cracking product to the dilute acid solution is 10-20: 1.
Preferably, the cracking catalyst is carbon nanotube-supported potassium oxide.
Preferably, the impurity removal material is modified WS2Grafting to metal-organic frameworks to form WS2-an organic framework composite.
Preferably, the metal-organic framework compound is a zirconium-based metal-organic framework compound.
Preferably, the preparation method of the metal-organic framework compound comprises the following steps:
weighing ZrCl4Adding into deionized water, stirring to dissolve completely to obtain ZrCl4A solution; adding terephthalic acid into N, N-dimethylformamide, and stirring uniformly to obtain a terephthalic acid solution; wherein ZrCl4The solid-to-liquid ratio of the deionized water is 1: 10-15; the mass ratio of the terephthalic acid to the N, N-dimethylformamide is 1: 3-5;
reacting the ZrCl4Dropwise adding the solution into a terephthalic acid solution, stirring while dropwise adding, continuously stirring for 0.5-1 h after completely dropwise adding, pouring into a reaction kettle with a polytetrafluoroethylene lining, sealing, placing in a drying oven at 150-180 ℃, reacting for 8-12 h, cooling, filtering, washing with deionized water for 3 times, washing with ethanol for 3 times, drying at 80-90 ℃, and grinding to powder to obtain a metal organic framework compound; wherein, the ZrCl4The volume ratio of the solution to the terephthalic acid solution is 3-5: 1.
Preferably, said WS2The modification method comprises the following steps:
s1, weighing WS2Mixing the nanosheets with 98% concentrated sulfuric acid by mass, stirring uniformly in an ice-water bath, adding potassium ferrate, stirring and reacting for 0.2-0.6 h, heating to 45-50 ℃, and stirring again for 0.2-0.6 h to obtain a reaction solution A; wherein WS2The solid-liquid ratio of the nanosheets to concentrated sulfuric acid is 1: 15-20; potassium ferrate and WS2The mass ratio of the nano sheets is 2-3: 1, and the stirring speed is 200-300 rpm;
s2, adding deionized water into the reaction liquid A, heating to 80-100 ℃, stirring for 0.2-0.6 h, and then respectively adding Al (NO)3)3And Mg (NO)3)3Stirring and reacting for 1-3 h to obtain a reaction solution B; wherein the volume ratio of the reaction liquid A to the deionized water is 1: 2-3; al (NO)3)3And WS2The mass ratio of the nano sheets is 1: 2-3; mg (NO)3)3And WS2The mass ratio of the nano sheets is 1: 2-3, the stirring speed is 300-500 rpm;
s3, pouring the reaction liquid B into deionized water at 0-10 ℃ while the reaction liquid B is hot, adding hydrogen peroxide, stirring uniformly, standing for 1-2 h, filtering to obtain a solid, washing for 3 times by using saturated sodium carbonate, then washing to be neutral by using deionized water, drying in an oven at 80-90 ℃, and crushing in a nano crusher to obtain the modified WS2Nano powder; wherein the volume ratio of the reaction liquid B to deionized water at 0-10 ℃ is 1: 2-3; the volume ratio of the hydrogen peroxide to the reaction liquid B is 1: 5-10; the stirring speed is 300-500 rpm.
Preferably, said WS2The preparation method of the organic framework composite material comprises the following steps:
(1) weighing the modified WS2Adding the nano powder into deionized water, stirring uniformly, and performing ultrasonic treatment for 1-2 hours to obtain a liquid M; adding cetyl trimethyl ammonium bromide into deionized water, stirring uniformly, and then dropwise adding 0.1mol/L NaOH solution until the pH value is 11.0-12.0 to obtain liquid N; slowly pouring the liquid N into the liquid M while stirring, carrying out ultrasonic treatment for 1-2 h after the liquid N is completely poured into the liquid M, and then placing the liquid N in a water bath condition at 50-60 ℃ for reaction for 3-5 h to obtain WS2Pretreatment liquid;
(2)WS2load graft to organic framework composite:
adding a metal organic framework compound into deionized water, stirring until the mixture is uniform, and slowly adding the mixture into the WS2Continuously reacting the pretreatment liquid for 10-15 h under the condition of 50-60 ℃ water bath, cooling to room temperature, centrifuging to obtain a solid, washing with deionized water for 3 times, then washing with chloroform for 3 times, and drying at 80-90 ℃ to obtain the organic framework material load WS2Pretreating a substance;
(3) organic framework material loading WS2The post-treatment:
loading WS on the organic framework material2Placing the pre-treated substance in a graphite furnace, vacuumizing, introducing a mixed gas of hydrogen and helium to atmospheric pressure, heating to 250 ℃ at a speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at a speed of 10 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain a solid C; grinding the solid C into powder, mixing with excessive absolute ethyl alcohol, stirring for 0.5-1 h, filtering to obtain a solid, and drying in an oven at 60-70 ℃ to obtain the product WS2-an organic framework composite.
The invention has the beneficial effects that:
1. according to the process method, the waste plant oil is pretreated firstly, the finally obtained pretreated matter is relatively pure, more than 95% of impurities and pigments are removed, guarantee is provided for subsequent cracking purification and reduction of equipment faults, and the service cycle of the equipment is prolonged; the second step belongs to the cracking process, the pretreated plant waste oil is treated by a catalytic cracking method, and the obtained cracking product has light color and good smell and can meet the market demand; the third step belongs to the post-treatment process of the second step cracking, and dilute acid is added during the post-treatment process to convert the salts generated by the second step cracking into acid, so that the purification of the fourth step is facilitated; the rectification tower with high-efficiency separation capacity is used for the oleic acid purification in the fourth step, so that the purification efficiency is improved.
2. During pretreatment, large blocks and impurities with large mass are firstly filtered by standing, then diluted acid solution is added for treatment, so that some impurities dissolved in grease are removed by diluted acid, and then the residual impurities which are not treated and are not cleaned are adsorbed by using impurity removing materials. Wherein the impurity-removing material is WS2-an organic framework composite; the preparation process of the material comprises the steps of preparing the zirconium-based organic framework and then carrying out WS treatment2Modifying the modified WS2Capable of being loaded and grafted on a zirconium-based organic framework and then grafting WS to the load2The zirconium-based organic framework is subjected to post-treatment in a high-temperature environment and H2The heat reduction treatment is carried out in the environment of/He gas, and the obvious reduction in the processWS2The oxygen-containing functional group number on the surface can still be combined with the grafting of the organic framework material, thereby effectively ensuring WS2-integrity of the organic framework composite clad structure.
3. The catalyst used in the cracking process is carbon nanotube loaded potassium oxide, and the catalyst has high catalytic activity, is pollution-free in the whole process and is environment-friendly. The preparation of the catalyst also adopts a simple and green process to successfully prepare the carbon nano tube loaded high-activity potassium oxide catalyst. When the catalyst is used, the yield of the product can reach more than 97%, and the catalyst can be recycled after simple treatment. According to the experimental result of the invention, after the potassium ion leaching agent is repeatedly used for 5 times, the leaching rate of potassium ions is still lower than 0.1mg/L and is far lower than the maximum limit value of 5mg/L specified by international standards.
4. The impurity removing material prepared by the invention can be quickly and uniformly distributed in the vegetable oil within a certain concentration range without forming agglomeration, on one hand, the WS is used2Modified and grafted on the surface of the organic framework material to ensure that the surface of the organic framework material contains hydroxyl which can reduce the crosslinking density of vegetable oil, thereby WS2The flexural modulus of the organic framework composite in greases will be much lower than the organic framework material alone or the unmodified WS2Flexural modulus in grease; another aspect is WS2The hydrophobic substance has the structural characteristics changed after being modified so as to have the surface activity effect, so that the hydrophobic substance has the surface activity effect in WS2After dispersion of the organic framework composite in the oil, WS2The oil-water microemulsion can adsorb a small amount of water in the oil and fat so as to be positioned at an oil-water two-phase interface to form a water-in-oil microemulsion, so that the oil-water microemulsion can be uniformly dispersed in the oil and fat and is easier to separate subsequently. Furthermore, WS2Magnesium and aluminum are also introduced during the modification process, the two elements being introduced in view of WS2Special layer structure, thereby WS2Magnesium ions and aluminum ions are introduced into the interlayer position of the layered structure, so that the capability of adsorbing impurities and pigments is greatly improved.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A process method for producing oleic acid by using plant waste oil comprises the following steps:
first, pretreatment
Firstly, standing and settling vegetable waste oil for 10-12 hours, reserving upper-layer oil, and removing bottom impurities to obtain primary filtered oil; filtering the primary filtered oil to remove suspended and floating impurities to obtain secondary filtered oil;
adding a dilute acid solution into the second-stage filtered oil, stirring the mixture uniformly, then placing the mixture into a settling reaction kettle for settling for 1-2 hours, and filtering to obtain third-stage filtered oil;
pouring impurity-removing materials into the tertiary filtering grease, stirring for 2-3 h, and filtering again to obtain a pretreated substance;
second, cracking
Adding a cracking catalyst into the pretreated substance, starting stirring, and cracking to obtain a cracking product; wherein the cracking temperature is 200-230 ℃, the cracking pressure is 1.8-2.3 MPa, and the stirring speed is 200-500 rpm;
third, post-treatment
Adding the dilute acid solution into the cracked product again, heating to 60-70 ℃, and stirring for 2-5 hours to obtain a post-treated product;
the fourth step, purification
Purifying the post-treated substance by adopting a 5-tower series rectification process to obtain oleic acid; wherein the temperature of the rectifying tower is 230-260 ℃, and the pressure of the top of the rectifying tower is 0.2-0.5 kPa.
Wherein the solution is a sulfuric acid aqueous solution with the concentration of 0.1 mol/L; the volume ratio of the secondary filtering oil to the dilute acid solution is 10-50: 1; the volume ratio of the cracking product to the dilute acid solution is 10-20: 1; the decomposing catalyst is carbon nanotube loaded potassium oxide.
The impurity-removing material is modified WS2Grafting to metal-organic frameworks to form WS2-an organic framework composite; the metal-organic framework compound is a zirconium-based metal-organic frameworkA compound (I) is provided.
The preparation method of the metal organic framework compound comprises the following steps:
weighing ZrCl4Adding into deionized water, stirring to dissolve completely to obtain ZrCl4A solution; adding terephthalic acid into N, N-dimethylformamide, and stirring uniformly to obtain a terephthalic acid solution; wherein ZrCl4The solid-to-liquid ratio of the deionized water is 1: 12; the mass ratio of terephthalic acid to N, N-dimethylformamide is 1: 4;
reacting ZrCl4Dropwise adding the solution into a terephthalic acid solution, stirring while dropwise adding, continuously stirring for 0.5-1 h after completely dropwise adding, pouring into a reaction kettle with a polytetrafluoroethylene lining, sealing, placing in a drying oven at 150-180 ℃, reacting for 8-12 h, cooling, filtering, washing with deionized water for 3 times, washing with ethanol for 3 times, drying at 80-90 ℃, and grinding to powder to obtain a metal organic framework compound; wherein ZrCl4The volume ratio of the solution to the terephthalic acid solution was 4: 1.
Wherein WS2The modification method comprises the following steps:
s1, weighing WS2Mixing the nanosheets with 98% concentrated sulfuric acid by mass, stirring uniformly in an ice-water bath, adding potassium ferrate, stirring and reacting for 0.2-0.6 h, heating to 45-50 ℃, and stirring again for 0.2-0.6 h to obtain a reaction solution A; wherein WS2The solid-liquid ratio of the nanosheets to concentrated sulfuric acid is 1: 18; potassium ferrate and WS2The mass ratio of the nano sheets is 2.5:1, and the stirring speed is 200-300 rpm;
s2, adding deionized water into the reaction liquid A, heating to 80-100 ℃, stirring for 0.2-0.6 h, and then respectively adding Al (NO)3)3And Mg (NO)3)3Stirring and reacting for 1-3 h to obtain a reaction solution B; wherein the volume ratio of the reaction liquid A to the deionized water is 1: 2.5; al (NO)3)3And WS2The mass ratio of the nano sheets is 1: 2.5; mg (NO)3)3And WS2The mass ratio of the nano sheets is 1:2.5, the stirring speed is 300-500 rpm;
s3, pouring the reaction liquid B into deionized water at 0-10 ℃ while the reaction liquid B is hotAdding hydrogen peroxide, stirring uniformly, standing for 1-2 h, filtering to obtain a solid, washing for 3 times by using saturated sodium carbonate, washing to be neutral by using deionized water, drying in an oven at 80-90 ℃, and crushing in a nano crusher to obtain the modified WS2Nano powder; wherein the volume ratio of the reaction liquid B to the deionized water at 0-10 ℃ is 1: 2.5; the volume ratio of the hydrogen peroxide to the reaction liquid B is 1: 8; the stirring speed is 300-500 rpm.
WS2The preparation method of the organic framework composite material comprises the following steps:
(1) weighing modified WS2Adding the nano powder into deionized water, stirring uniformly, and performing ultrasonic treatment for 1-2 hours to obtain a liquid M; adding cetyl trimethyl ammonium bromide into deionized water, stirring uniformly, and then dropwise adding 0.1mol/L NaOH solution until the pH value is 11.0-12.0 to obtain liquid N; slowly pouring the liquid N into the liquid M while stirring, carrying out ultrasonic treatment for 1.5h after the liquid N is completely poured into the liquid M, and then placing the liquid N in a water bath at the temperature of 50-60 ℃ for reaction for 4h to obtain WS2Pretreatment liquid;
(2)WS2load graft to organic framework composite:
adding the metal organic framework compound into deionized water, stirring the mixture until the mixture is uniform, and slowly adding the mixture to WS2Continuously reacting the pretreatment liquid for 10-15 h under the condition of 50-60 ℃ water bath, cooling to room temperature, centrifuging to obtain a solid, washing with deionized water for 3 times, then washing with chloroform for 3 times, and drying at 80-90 ℃ to obtain the organic framework material load WS2Pretreating a substance;
(3) organic framework material loading WS2The post-treatment:
loading organic frame material with WS2Placing the pre-treated substance in a graphite furnace, vacuumizing, introducing a mixed gas of hydrogen and helium to atmospheric pressure, heating to 250 ℃ at a speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at a speed of 10 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain a solid C; grinding the solid C into powder, mixing with excessive absolute ethyl alcohol, stirring for 0.5-1 h, filtering to obtain a solid, and drying in an oven at 60-70 ℃ to obtain the product WS2-is provided withA machine frame composite.
Example 2
A process method for producing oleic acid by using plant waste oil comprises the following steps:
first, pretreatment
Firstly, standing and settling vegetable waste oil for 10-12 hours, reserving upper-layer oil, and removing bottom impurities to obtain primary filtered oil; filtering the primary filtered oil to remove suspended and floating impurities to obtain secondary filtered oil;
adding a dilute acid solution into the second-stage filtered oil, stirring the mixture uniformly, then placing the mixture into a settling reaction kettle for settling for 1-2 hours, and filtering to obtain third-stage filtered oil;
pouring impurity-removing materials into the tertiary filtering grease, stirring for 2-3 h, and filtering again to obtain a pretreated substance;
second, cracking
Adding a cracking catalyst into the pretreated substance, starting stirring, and cracking to obtain a cracking product; wherein the cracking temperature is 200-230 ℃, the cracking pressure is 1.8-2.3 MPa, and the stirring speed is 200-500 rpm;
third, post-treatment
Adding the dilute acid solution into the cracked product again, heating to 60-70 ℃, and stirring for 2-5 hours to obtain a post-treated product;
the fourth step, purification
Purifying the post-treated substance by adopting a 5-tower series rectification process to obtain oleic acid; wherein the temperature of the rectifying tower is 230-260 ℃, and the pressure of the top of the rectifying tower is 0.2-0.5 kPa.
Wherein the solution is a sulfuric acid aqueous solution with the concentration of 0.1 mol/L; the volume ratio of the secondary filtering oil to the dilute acid solution is 10-50: 1; the volume ratio of the cracking product to the dilute acid solution is 10-20: 1; the decomposing catalyst is carbon nanotube loaded potassium oxide.
The impurity-removing material is modified WS2Grafting to metal-organic frameworks to form WS2-an organic framework composite; the metal-organic framework compound is a zirconium-based metal-organic framework compound.
The preparation method of the metal organic framework compound comprises the following steps:
weighing ZrCl4Adding into deionized water, stirring to dissolve completely to obtain ZrCl4A solution; adding terephthalic acid into N, N-dimethylformamide, and stirring uniformly to obtain a terephthalic acid solution; wherein ZrCl4The solid-to-liquid ratio of the deionized water is 1: 10-15; the mass ratio of terephthalic acid to N, N-dimethylformamide is 1: 3;
reacting ZrCl4Dropwise adding the solution into a terephthalic acid solution, stirring while dropwise adding, continuously stirring for 0.5-1 h after completely dropwise adding, pouring into a reaction kettle with a polytetrafluoroethylene lining, sealing, placing in a drying oven at 150-180 ℃, reacting for 8-12 h, cooling, filtering, washing with deionized water for 3 times, washing with ethanol for 3 times, drying at 80-90 ℃, and grinding to powder to obtain a metal organic framework compound; wherein ZrCl4The volume ratio of the solution to the terephthalic acid solution was 3: 1.
Wherein WS2The modification method comprises the following steps:
s1, weighing WS2Mixing the nanosheets with 98% concentrated sulfuric acid by mass, stirring uniformly in an ice-water bath, adding potassium ferrate, stirring and reacting for 0.2-0.6 h, heating to 45-50 ℃, and stirring again for 0.2-0.6 h to obtain a reaction solution A; wherein WS2The solid-liquid ratio of the nanosheets to concentrated sulfuric acid is 1: 15; potassium ferrate and WS2The mass ratio of the nanosheets is 2:1, and the stirring speed is 200-300 rpm;
s2, adding deionized water into the reaction liquid A, heating to 80-100 ℃, stirring for 0.2-0.6 h, and then respectively adding Al (NO)3)3And Mg (NO)3)3Stirring and reacting for 1-3 h to obtain a reaction solution B; wherein the volume ratio of the reaction liquid A to the deionized water is 1: 2; al (NO)3)3And WS2The mass ratio of the nano sheets is 1: 2; mg (NO)3)3And WS2The mass ratio of the nano sheets is 1:2, the stirring speed is 300-500 rpm;
s3, pouring the reaction liquid B into deionized water at 0-10 ℃ while the reaction liquid B is hot, adding hydrogen peroxide, stirring uniformly, and standingFiltering for 1-2 h to obtain a solid, washing the solid for 3 times by using saturated sodium carbonate, then washing the solid to be neutral by using deionized water, drying the solid in an oven at the temperature of 80-90 ℃, and crushing the solid in a nano crusher to obtain the modified WS2Nano powder; wherein the volume ratio of the reaction liquid B to deionized water at 0-10 ℃ is 1: 2; the volume ratio of the hydrogen peroxide to the reaction liquid B is 1: 5; the stirring speed is 300-500 rpm.
WS2The preparation method of the organic framework composite material comprises the following steps:
(1) weighing modified WS2Adding the nano powder into deionized water, stirring uniformly, and performing ultrasonic treatment for 1-2 hours to obtain a liquid M; adding cetyl trimethyl ammonium bromide into deionized water, stirring uniformly, and then dropwise adding 0.1mol/L NaOH solution until the pH value is 11.0-12.0 to obtain liquid N; slowly pouring the liquid N into the liquid M while stirring, carrying out ultrasonic treatment for 1h after the liquid N is completely poured into the liquid M, and then carrying out reaction for 3h in a water bath at 50-60 ℃ to obtain WS2Pretreatment liquid;
(2)WS2load graft to organic framework composite:
adding the metal organic framework compound into deionized water, stirring the mixture until the mixture is uniform, and slowly adding the mixture to WS2Continuously reacting the pretreatment liquid for 10-15 h under the condition of 50-60 ℃ water bath, cooling to room temperature, centrifuging to obtain a solid, washing with deionized water for 3 times, then washing with chloroform for 3 times, and drying at 80-90 ℃ to obtain the organic framework material load WS2Pretreating a substance;
(2) organic framework material loading WS2The post-treatment:
loading organic frame material with WS2Placing the pre-treated substance in a graphite furnace, vacuumizing, introducing a mixed gas of hydrogen and helium to atmospheric pressure, heating to 250 ℃ at a speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at a speed of 10 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain a solid C; grinding the solid C into powder, mixing with excessive absolute ethyl alcohol, stirring for 0.5-1 h, filtering to obtain a solid, and drying in an oven at 60-70 ℃ to obtain the product WS2-an organic framework composite.
Example 3
A process method for producing oleic acid by using plant waste oil comprises the following steps:
first, pretreatment
Firstly, standing and settling vegetable waste oil for 10-12 hours, reserving upper-layer oil, and removing bottom impurities to obtain primary filtered oil; filtering the primary filtered oil to remove suspended and floating impurities to obtain secondary filtered oil;
adding a dilute acid solution into the second-stage filtered oil, stirring the mixture uniformly, then placing the mixture into a settling reaction kettle for settling for 1-2 hours, and filtering to obtain third-stage filtered oil;
pouring impurity-removing materials into the tertiary filtering grease, stirring for 2-3 h, and filtering again to obtain a pretreated substance;
second, cracking
Adding a cracking catalyst into the pretreated substance, starting stirring, and cracking to obtain a cracking product; wherein the cracking temperature is 200-230 ℃, the cracking pressure is 1.8-2.3 MPa, and the stirring speed is 200-500 rpm;
third, post-treatment
Adding the dilute acid solution into the cracked product again, heating to 60-70 ℃, and stirring for 2-5 hours to obtain a post-treated product;
the fourth step, purification
Purifying the post-treated substance by adopting a 5-tower series rectification process to obtain oleic acid; wherein the temperature of the rectifying tower is 230-260 ℃, and the pressure of the top of the rectifying tower is 0.2-0.5 kPa.
Wherein the solution is a sulfuric acid aqueous solution with the concentration of 0.1 mol/L; the volume ratio of the secondary filtering oil to the dilute acid solution is 10-50: 1; the volume ratio of the cracking product to the dilute acid solution is 10-20: 1; the decomposing catalyst is carbon nanotube loaded potassium oxide.
The impurity-removing material is modified WS2Grafting to metal-organic frameworks to form WS2-an organic framework composite; the metal-organic framework compound is a zirconium-based metal-organic framework compound.
The preparation method of the metal organic framework compound comprises the following steps:
weighing ZrCl4Adding into deionized water, stirring to dissolve completely to obtain ZrCl4A solution; adding terephthalic acid into N, N-dimethylformamide, and stirring uniformly to obtain a terephthalic acid solution; wherein ZrCl4The solid-to-liquid ratio of the deionized water is 1: 15; the mass ratio of terephthalic acid to N, N-dimethylformamide is 1: 5;
reacting ZrCl4Dropwise adding the solution into a terephthalic acid solution, stirring while dropwise adding, continuously stirring for 0.5-1 h after completely dropwise adding, pouring into a reaction kettle with a polytetrafluoroethylene lining, sealing, placing in a drying oven at 150-180 ℃, reacting for 8-12 h, cooling, filtering, washing with deionized water for 3 times, washing with ethanol for 3 times, drying at 80-90 ℃, and grinding to powder to obtain a metal organic framework compound; wherein ZrCl4The volume ratio of the solution to the terephthalic acid solution was 5: 1.
Wherein WS2The modification method comprises the following steps:
s1, weighing WS2Mixing the nanosheets with 98% concentrated sulfuric acid by mass, stirring uniformly in an ice-water bath, adding potassium ferrate, stirring and reacting for 0.2-0.6 h, heating to 45-50 ℃, and stirring again for 0.2-0.6 h to obtain a reaction solution A; wherein WS2The solid-liquid ratio of the nanosheets to concentrated sulfuric acid is 1: 20; potassium ferrate and WS2The mass ratio of the nano sheets is 3:1, and the stirring speed is 200-300 rpm;
s2, adding deionized water into the reaction liquid A, heating to 80-100 ℃, stirring for 0.2-0.6 h, and then respectively adding Al (NO)3)3And Mg (NO)3)3Stirring and reacting for 1-3 h to obtain a reaction solution B; wherein the volume ratio of the reaction liquid A to the deionized water is 1: 3; al (NO)3)3And WS2The mass ratio of the nano sheets is 1: 3; mg (NO)3)3And WS2The mass ratio of the nano sheets is 1:3, stirring at the speed of 300-500 rpm;
s3, pouring the reaction liquid B into deionized water at 0-10 ℃ while the reaction liquid B is hot, adding hydrogen peroxide, stirring uniformly, standing for 1-2 h, filtering to obtain a solid, and washing with saturated sodium carbonateWashing for 3 times, washing with deionized water to neutrality, drying in an oven at 80-90 deg.C, and pulverizing in a nanometer pulverizer to obtain modified WS2Nano powder; wherein the volume ratio of the reaction liquid B to deionized water at 0-10 ℃ is 1: 3; the volume ratio of the hydrogen peroxide to the reaction liquid B is 1: 10; the stirring speed is 300-500 rpm.
WS2The preparation method of the organic framework composite material comprises the following steps:
(1) weighing modified WS2Adding the nano powder into deionized water, stirring uniformly, and performing ultrasonic treatment for 1-2 hours to obtain a liquid M; adding cetyl trimethyl ammonium bromide into deionized water, stirring uniformly, and then dropwise adding 0.1mol/L NaOH solution until the pH value is 11.0-12.0 to obtain liquid N; slowly pouring the liquid N into the liquid M while stirring, carrying out ultrasonic treatment for 2h after the liquid N is completely poured into the liquid M, and then carrying out reaction for 5h in a water bath at 50-60 ℃ to obtain WS2Pretreatment liquid;
(2)WS2load graft to organic framework composite:
adding the metal organic framework compound into deionized water, stirring the mixture until the mixture is uniform, and slowly adding the mixture to WS2Continuously reacting the pretreatment liquid for 10-15 h under the condition of 50-60 ℃ water bath, cooling to room temperature, centrifuging to obtain a solid, washing with deionized water for 3 times, then washing with chloroform for 3 times, and drying at 80-90 ℃ to obtain the organic framework material load WS2Pretreating a substance;
(2) organic framework material loading WS2The post-treatment:
loading organic frame material with WS2Placing the pre-treated substance in a graphite furnace, vacuumizing, introducing a mixed gas of hydrogen and helium to atmospheric pressure, heating to 250 ℃ at a speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at a speed of 10 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain a solid C; grinding the solid C into powder, mixing with excessive absolute ethyl alcohol, stirring for 0.5-1 h, filtering to obtain a solid, and drying in an oven at 60-70 ℃ to obtain the product WS2-an organic framework composite.
Comparative example 1
A process method for producing oleic acid by using plant waste oil comprises the following steps:
first, pretreatment
Firstly, standing and settling vegetable waste oil for 10-12 hours, reserving upper-layer oil, and removing bottom impurities to obtain primary filtered oil; filtering the primary filtered oil to remove suspended and floating impurities to obtain secondary filtered oil;
adding a dilute acid solution into the second-stage filtered oil, stirring the mixture uniformly, then placing the mixture into a settling reaction kettle for settling for 1-2 hours, and filtering to obtain third-stage filtered oil;
pouring impurity-removing materials into the tertiary filtering grease, stirring for 2-3 h, and filtering again to obtain a pretreated substance;
second, cracking
Adding a cracking catalyst into the pretreated substance, starting stirring, and cracking to obtain a cracking product; wherein the cracking temperature is 200-230 ℃, the cracking pressure is 1.8-2.3 MPa, and the stirring speed is 200-500 rpm;
third, post-treatment
Adding the dilute acid solution into the cracked product again, heating to 60-70 ℃, and stirring for 2-5 hours to obtain a post-treated product;
the fourth step, purification
Purifying the post-treated substance by adopting a 5-tower series rectification process to obtain oleic acid; wherein the temperature of the rectifying tower is 230-260 ℃, and the pressure of the top of the rectifying tower is 0.2-0.5 kPa.
Wherein the solution is a sulfuric acid aqueous solution with the concentration of 0.1 mol/L; the volume ratio of the secondary filtering oil to the dilute acid solution is 10-50: 1; the volume ratio of the cracking product to the dilute acid solution is 10-20: 1; the cracking catalyst is carbon nanotube loaded potassium oxide.
The impurity removal material is a metal organic framework compound; the metal-organic framework compound is a zirconium-based metal-organic framework compound.
The preparation method of the metal organic framework compound comprises the following steps:
weighing ZrCl4Adding into deionized water, stirring to dissolve completely to obtain ZrCl4A solution; adding terephthalic acid into N, N-dimethylformamide, and stirring uniformly to obtain a terephthalic acid solution; wherein ZrCl4The solid-to-liquid ratio of the deionized water is 1: 12; the mass ratio of terephthalic acid to N, N-dimethylformamide is 1: 4;
reacting ZrCl4Dropwise adding the solution into a terephthalic acid solution, stirring while dropwise adding, continuously stirring for 0.5-1 h after completely dropwise adding, pouring into a reaction kettle with a polytetrafluoroethylene lining, sealing, placing in a drying oven at 150-180 ℃, reacting for 8-12 h, cooling, filtering, washing with deionized water for 3 times, washing with ethanol for 3 times, drying at 80-90 ℃, and grinding to powder to obtain a metal organic framework compound; wherein ZrCl4The volume ratio of the solution to the terephthalic acid solution was 4: 1.
Comparative example 2
A process method for producing oleic acid by using plant waste oil comprises the following steps:
first, pretreatment
Firstly, standing and settling vegetable waste oil for 10-12 hours, reserving upper-layer oil, and removing bottom impurities to obtain primary filtered oil; filtering the primary filtered oil to remove suspended and floating impurities to obtain secondary filtered oil;
adding a dilute acid solution into the second-stage filtered oil, stirring the mixture uniformly, then placing the mixture into a settling reaction kettle for settling for 1-2 hours, and filtering to obtain third-stage filtered oil;
pouring impurity-removing materials into the tertiary filtering grease, stirring for 2-3 h, and filtering again to obtain a pretreated substance;
second, cracking
Adding a cracking catalyst into the pretreated substance, starting stirring, and cracking to obtain a cracking product; wherein the cracking temperature is 200-230 ℃, the cracking pressure is 1.8-2.3 MPa, and the stirring speed is 200-500 rpm;
third, post-treatment
Adding the dilute acid solution into the cracked product again, heating to 60-70 ℃, and stirring for 2-5 hours to obtain a post-treated product;
the fourth step, purification
Purifying the post-treated substance by adopting a 5-tower series rectification process to obtain oleic acid; wherein the temperature of the rectifying tower is 230-260 ℃, and the pressure of the top of the rectifying tower is 0.2-0.5 kPa.
Wherein the solution is a sulfuric acid aqueous solution with the concentration of 0.1 mol/L; the volume ratio of the secondary filtering oil to the dilute acid solution is 10-50: 1; the volume ratio of the cracking product to the dilute acid solution is 10-20: 1; the cracking catalyst is calcium oxide.
The impurity removal material is a metal organic framework compound; the metal-organic framework compound is a zirconium-based metal-organic framework compound.
The preparation method of the metal organic framework compound comprises the following steps:
weighing ZrCl4Adding into deionized water, stirring to dissolve completely to obtain ZrCl4A solution; adding terephthalic acid into N, N-dimethylformamide, and stirring uniformly to obtain a terephthalic acid solution; wherein ZrCl4The solid-to-liquid ratio of the deionized water is 1: 12; the mass ratio of terephthalic acid to N, N-dimethylformamide is 1: 4;
reacting ZrCl4Dropwise adding the solution into a terephthalic acid solution, stirring while dropwise adding, continuously stirring for 0.5-1 h after completely dropwise adding, pouring into a reaction kettle with a polytetrafluoroethylene lining, sealing, placing in a drying oven at 150-180 ℃, reacting for 8-12 h, cooling, filtering, washing with deionized water for 3 times, washing with ethanol for 3 times, drying at 80-90 ℃, and grinding to powder to obtain a metal organic framework compound; wherein ZrCl4The volume ratio of the solution to the terephthalic acid solution was 4: 1.
Comparative example 3
A process method for producing oleic acid by using plant waste oil comprises the following steps:
first, pretreatment
Firstly, standing and settling vegetable waste oil for 10-12 hours, reserving upper-layer oil, and removing bottom impurities to obtain primary filtered oil; filtering the primary filtered oil to remove suspended and floating impurities to obtain secondary filtered oil;
adding a dilute acid solution into the second-stage filtered grease, stirring the mixture uniformly, then placing the mixture into a settling reaction kettle for settling for 1-2 hours, and filtering the mixture to obtain a pretreated substance;
second, cracking
Adding a cracking catalyst into the pretreated substance, starting stirring, and cracking to obtain a cracking product; wherein the cracking temperature is 200-230 ℃, the cracking pressure is 1.8-2.3 MPa, and the stirring speed is 200-500 rpm;
third, post-treatment
Adding the dilute acid solution into the cracked product again, heating to 60-70 ℃, and stirring for 2-5 hours to obtain a post-treated product;
the fourth step, purification
Purifying the post-treated substance by adopting a 5-tower series rectification process to obtain oleic acid; wherein the temperature of the rectifying tower is 230-260 ℃, and the pressure of the top of the rectifying tower is 0.2-0.5 kPa.
Wherein the solution is a sulfuric acid aqueous solution with the concentration of 0.1 mol/L; the volume ratio of the secondary filtering oil to the dilute acid solution is 10-50: 1; the volume ratio of the cracking product to the dilute acid solution is 10-20: 1; the decomposing catalyst is carbon nanotube loaded potassium oxide.
In order to more clearly illustrate the present invention, the results of testing the oleic acids prepared in examples 1 to 3 and comparative examples 1 to 3 of the present invention are shown in table 1.
TABLE 1 results of oleic acid assay
As can be seen from Table 1, the oleic acid prepared in the examples 1 to 3 of the present invention has saponification value, acid value, moisture content and inorganic acid content all meeting the national standard (the oleic acid saponification value is 195 to 205mgKOH/g qualified product according to the national standard), and is a product with better quality, while the comparative examples 1 to 3 are far inferior to the examples 1 to 3 of the present invention in quality.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (3)
1. A process method for producing oleic acid by using plant waste oil is characterized by comprising the following steps:
first, pretreatment
Firstly, standing and settling vegetable waste oil for 10-12 hours, reserving upper-layer oil, and removing bottom impurities to obtain primary filtered oil; filtering the primary filtered oil to remove suspended and floating impurities to obtain secondary filtered oil;
adding a dilute acid solution into the second-stage filtered grease, stirring the mixture uniformly, then placing the mixture into a settling reaction kettle for settling for 1-2 hours, and filtering the mixture to obtain third-stage filtered grease;
pouring impurity-removing materials into the three-stage filtering grease, stirring for 2-3 h, and filtering again to obtain a pretreated substance;
second, cracking
Adding a cracking catalyst into the pretreated substance, starting stirring, and cracking to obtain a cracking product; wherein the cracking temperature is 200-230 ℃, the cracking pressure is 1.8-2.3 MPa, and the stirring speed is 200-500 rpm;
third, post-treatment
Adding a dilute acid solution into the cracked product again, heating to 60-70 ℃, and stirring for 2-5 hours to obtain a post-treated product;
the fourth step, purification
Purifying the post-treatment substance by adopting a 5-tower series rectification process to obtain oleic acid; wherein the temperature of the rectifying tower is 230-260 ℃, and the pressure of the top of the rectifying tower is 0.2-0.5 kPa;
the impurity removing material is modified WS2Grafting to metal-organic frameworks to form WS2-an organic framework composite;
the metal organic framework compound is a zirconium-based metal organic framework compound;
the preparation method of the metal organic framework compound comprises the following steps:
weighing ZrCl4Adding into deionized water, stirring to dissolve completely to obtain ZrCl4A solution; adding terephthalic acid into N, N-dimethylformamide, and stirring uniformly to obtain a terephthalic acid solution; wherein ZrCl4The solid-to-liquid ratio of the deionized water is 1: 10-15; the mass ratio of the terephthalic acid to the N, N-dimethylformamide is 1: 3-5;
reacting the ZrCl4Dropwise adding the solution into a terephthalic acid solution, stirring while dropwise adding, continuously stirring for 0.5-1 h after completely dropwise adding, pouring into a reaction kettle with a polytetrafluoroethylene lining, sealing, placing in a drying oven at 150-180 ℃, reacting for 8-12 h, cooling, filtering, washing with deionized water for 3 times, washing with ethanol for 3 times, drying at 80-90 ℃, and grinding to powder to obtain a metal organic framework compound; wherein, the ZrCl4The volume ratio of the solution to the terephthalic acid solution is 3-5: 1;
the WS2The modification method comprises the following steps:
s1, weighing WS2Mixing the nanosheets with 98% concentrated sulfuric acid by mass, stirring uniformly in an ice-water bath, adding potassium ferrate, stirring and reacting for 0.2-0.6 h, heating to 45-50 ℃, and stirring again for 0.2-0.6 h to obtain a reaction solution A; wherein WS2The solid-liquid ratio of the nanosheets to concentrated sulfuric acid is 1: 15-20; potassium ferrate and WS2The mass ratio of the nano sheets is 2-3: 1, and the stirring speed is 200-300 rpm;
s2, adding deionized water into the reaction liquid A, heating to 80-100 ℃, stirring for 0.2-0.6 h, and then respectively adding Al (NO)3)3And Mg (NO)3)3Stirring and reacting for 1-3 h to obtain a reaction solution B; wherein the volume ratio of the reaction liquid A to the deionized water is 1: 2-3; al (NO)3)3And WS2The mass ratio of the nano sheets is 1: 2-3; mg (NO)3)3And WS2The mass ratio of the nano sheets is 1: 2-3, the stirring speed is 300-500 rpm;
s3, inverting the mixturePouring the reaction solution B into deionized water at 0-10 ℃ while the reaction solution B is hot, adding hydrogen peroxide, stirring uniformly, standing for 1-2 h, filtering to obtain a solid, washing for 3 times by using saturated sodium carbonate, washing to be neutral by using deionized water, drying in an oven at 80-90 ℃, and crushing in a nano crusher to obtain the modified WS2Nano powder; wherein the volume ratio of the reaction liquid B to deionized water at 0-10 ℃ is 1: 2-3; the volume ratio of the hydrogen peroxide to the reaction liquid B is 1: 5-10; the stirring speed is 300-500 rpm;
the WS2The preparation method of the organic framework composite material comprises the following steps:
(1) weighing the modified WS2Adding the nano powder into deionized water, stirring uniformly, and performing ultrasonic treatment for 1-2 hours to obtain a liquid M; adding cetyl trimethyl ammonium bromide into deionized water, stirring uniformly, and then dropwise adding 0.1mol/L NaOH solution until the pH value is 11.0-12.0 to obtain liquid N; slowly pouring the liquid N into the liquid M while stirring, carrying out ultrasonic treatment for 1-2 h after the liquid N is completely poured into the liquid M, and then placing the liquid N in a water bath condition at 50-60 ℃ for reaction for 3-5 h to obtain WS2Pretreatment liquid;
(2)WS2load graft to organic framework composite:
adding a metal organic framework compound into deionized water, stirring until the mixture is uniform, and slowly adding the mixture into the WS2Continuously reacting the pretreatment liquid for 10-15 h under the condition of 50-60 ℃ water bath, cooling to room temperature, centrifuging to obtain a solid, washing with deionized water for 3 times, then washing with chloroform for 3 times, and drying at 80-90 ℃ to obtain the organic framework material load WS2Pretreating a substance;
(3) organic framework material loading WS2The post-treatment:
loading WS on the organic framework material2Placing the pre-treated substance in a graphite furnace, vacuumizing, introducing a mixed gas of hydrogen and helium to atmospheric pressure, heating to 250 ℃ at a speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at a speed of 10 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain a solid C; grinding the solid C into powder, and mixing with excessive anhydrous ethanolMixing and stirring for 0.5-1 h, filtering to obtain a solid, and drying in a drying oven at 60-70 ℃ to obtain a product WS2-an organic framework composite.
2. The process for producing oleic acid from waste vegetable oil according to claim 1, wherein the dilute acid solution is an aqueous solution of sulfuric acid having a concentration of 0.1 mol/L; the volume ratio of the secondary filtering oil to the dilute acid solution is 10-50: 1; the volume ratio of the cracking product to the dilute acid solution is 10-20: 1.
3. The process for producing oleic acid from waste vegetable oil as claimed in claim 1, wherein the cracking catalyst is carbon nanotube-supported potassium oxide.
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