CN102876462A - Method for preparing high-quality epoxidized soybean oil - Google Patents
Method for preparing high-quality epoxidized soybean oil Download PDFInfo
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- CN102876462A CN102876462A CN2012103888400A CN201210388840A CN102876462A CN 102876462 A CN102876462 A CN 102876462A CN 2012103888400 A CN2012103888400 A CN 2012103888400A CN 201210388840 A CN201210388840 A CN 201210388840A CN 102876462 A CN102876462 A CN 102876462A
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- 235000012424 soybean oil Nutrition 0.000 title claims abstract description 126
- 239000003549 soybean oil Substances 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 239000012074 organic phase Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 78
- 239000004593 Epoxy Substances 0.000 claims description 60
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 60
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- 235000019253 formic acid Nutrition 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 230000035484 reaction time Effects 0.000 claims description 21
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 235000019198 oils Nutrition 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 230000010349 pulsation Effects 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 abstract 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000002390 rotary evaporation Methods 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 22
- 239000005457 ice water Substances 0.000 description 12
- 229960000583 acetic acid Drugs 0.000 description 11
- 239000004800 polyvinyl chloride Substances 0.000 description 11
- 238000006735 epoxidation reaction Methods 0.000 description 10
- 229920000915 polyvinyl chloride Polymers 0.000 description 10
- 239000004902 Softening Agent Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 3
- 0 C*C(O*N(OC(*CN)=*)[Mn]OC(**)=O)=O Chemical compound C*C(O*N(OC(*CN)=*)[Mn]OC(**)=O)=O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- NWJXSVNLQJZDLV-UHFFFAOYSA-N formic acid;hydrogen peroxide Chemical compound OO.OC=O NWJXSVNLQJZDLV-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- -1 rhenium oxide-urea Chemical compound 0.000 description 1
- 230000001020 rhythmical effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Landscapes
- Fats And Perfumes (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses a method for preparing high-quality epoxidized soybean oil, comprising the following steps: mixing a hydrogen peroxide water solution and a formic acid water solution; then adding a catalyst and a stabilizing agent; pumping soybean oil and the mixture into a micro-channel modularized reaction device; keeping the reaction stopping time for 2-12 min; reacting at 65-95 DEG C and leading a reaction product into a separator; adding an NaCO3 water solution and statically standing to be layered to remove a water solution of the lower layer; washing an upper-layer organic phase by water; and carrying out rotary evaporation to obtain the high-quality epoxidized soybean oil. The preparation method of the high-quality epoxidized soybean oil disclosed by the invention is a continuous process; and the preparation process is easy to operate and control, the safety is high, the reaction conditions are moderate, the reaction stopping time is short, the quality of a product is stable and the epoxidized recycling rate is high. The method has the characteristics of simple production equipment, easiness for detaching and convenience for carrying and moving. The quantity of micro-channels can be simply increased and decreased to carry out convenient adjustment and an amplification effect which is similar with industrial production does not exist.
Description
Technical field
The present invention relates to prepare the method for epoxy soybean oil, belong to chemosynthesis technical field.
Background technology
PVC is as a kind of traditional general-purpose plastics, and it is of many uses, and consumption is very large.Wherein the flexible PVC product can be used for film article, electric wire, outer packaging.But all to add softening agent in the flexible PVC, to improve the performance of PVC.For a long time, the softening agent that uses in the PVC plastics industry mostly is phthalate.In China, the annual production of phthalic ester plasticizer and consumption all account for more than 80% of softening agent total amount, and epoxy soybean oil (ESO) is less than 10%.But owing to depositing the potential carinogenicity of phthalic ester plasticizer, strictly controlled its use abroad.China has also formulated relevant laws and rules, will progressively eliminate phthalate in the use of the aspects such as packaging material for food, medical apparatus and toy for children.And epoxy soybean oil is to use at present more nontoxic non-benzene class environment-friendly type plastic auxiliary agent-softening agent, it has the dual property of softening agent and thermostability concurrently, and nontoxic, safety and environmental protection, meet the RoHS of European Union environmental protection instruction and U.S. FDA foodstuff additive rule fully.
Epoxy soybean oil has a wide range of applications in the industry such as plastics, coating.This softening agent is except being widely used in plastic door-window, tubing, and upholstery material outside electric wire and the film, also can be used as and makes exigent filmstrip and the special softening agent that is used for gasket on the door of refrigerator.Because epoxy soybean oil has the satisfactory stability effect to light, heat, water tolerance and oil-proofness are also good, thereby can give the good physical strength of goods, weathering resistance and electrical property, and volatility is low, transport property is little.It not only has plastification to polyvinyl chloride, and the active chlorine atom on the polyvinyl chloride chain is stablized, can absorb rapidly the hydrogenchloride of degrading out because of light and heat, thereby the continuous decomposition of retardance polyvinyl chloride, play stable effect, and with polyvinyl chloride good consistency is arranged, almost can be used for all polrvinyl chloride products.Compare with other softening agent, another distinguishing feature of epoxy soybean oil is that its low temperature plasticity is very good.Add epoxy soybean oil in polyvinyl chloride (PVC) RESINS, can obviously play plastification under low temperature condition, plasticization effect is better than other common plasticizers.
Now up-to-date studies show that, epoxy soybean oil be good plasticizer for polyvinyl chloride still not, can also be used for other field.It is reported, epoxy soybean oil can be used for the intrinsic toughening modification of resol, thereby significantly improves the toughness of product.Other has report to show, epoxy soybean oil can be used for improving penetration of bitumens and ductility.In addition, about the research of epoxy soybean oil modified epoxy resin paint and adhesive for polyurethane also has report, epoxy soybean oil has played the effect that is highly profitable in the modifying process of epoxypaint and adhesive for polyurethane.Therefore, the range of application of epoxy soybean oil and development space will be day by day wide, and it also can meet protection of the environment fully as environmentfriendly products, to the requirement of human body toxicological harmless effect, are fit to the policy of China's Sustainable development, in China great development potentiality arranged.
The production method of tradition epoxy soybean oil mainly contains solvent method and solventless method.Solvent method uses benzene and substituted benzene as solvent, and sulfuric acid is as catalyzer.Environmental pollution is heavy, and Production Flow Chart is long, and equipment is many, and three wastes treatment capacity is large, and therefore poor product quality is eliminated substantially.Solventless method is substantially all adopted in now epoxy soybean oil production.The solventless method main technique is as the active oxygen carrier with formic acid or acetic acid, the 27-50% hydrogen peroxide is as the body of giving of oxygen, under the effect of catalyzer, carry out epoxidation reaction, in a certain temperature range, the epoxy agent is added drop-wise in the soybean oil, catalyzer commonly used has sulfuric acid, storng-acid cation exchange resin, the catalyzer of synthesizing epoxy soybean oil also has solid acid (such as Tai-Ace S 150, ferric sulfate), heteropolyacid, solid super-strong acid, molecular sieve etc. in addition.React complete by alkali cleaning, washing, dehydration obtains epoxy soybean oil at last.This method is compared with solvent method, and the technological process of production is shorter, and by product is few, pollutes and lacks, and three wastes processing cost is low, more meets the requirement of environmental protection, has therefore substantially replaced now solvent method, becomes the main method of now epoxy soybean oil production.Patent CN101691524A discloses a kind of method of method for preparing epoxidized soybean oil with high epoxy value by fractional step, in soybean oil, add hydrogen peroxide and formic acid in batches or step by step, react under the processing condition of strict control, obtain the epoxy soybean oil of high epoxy value, oxirane value reaches 6.9.But the anti-surface reaction that belongs to of this class epoxidation, the reaction times is longer, and the long reaction times will inevitably cause the by product of epoxy addition under acidic conditions, thereby oxirane value is difficult to reach more than 7.0.And the adding mode of peroxy acid is for add i.e. periodical operation in batches or step by step in the method that this patent adopts.Patent CN101445485A discloses the soybean oil epoxidizing method of a kind of less energy-consumption, few waste water, epoxidation systems is hydrogen peroxide-formic acid, its focus is the aftertreatment of crude product, reach the effect of falling acid and drying products with once washing again by wet distillation, reduce the generation of trade effluent; Patent CN101235021A then discloses the method that a kind of heteropolyacid catalyst prepares epoxy soybean oil, take solid-state heteropolyacid salt QYMO (HO) as catalyzer, do not add carboxylic acid, without protonic acid, solvent-free, the no acidic waste water of epoxidation process produces, but the oxirane value of product not high (oxirane value＜6.0); Patent CN10159158A discloses a kind of organic rhenium oxide-urea peroxide catalysis and has prepared the method for epoxy soybean oil, the method take urea peroxide as oxygen source, organic rhenium oxide is the active oxygen carrier, avoided simultaneously the use of carboxylic acid and strong acid, and obtained high epoxy value epoxy soybean oil (oxirane value＞7), but used catalyst system cost is higher, the urea peroxide large usage quantity is the 50%-100% of soybean oil quality, and produces a large amount of by product urea after the urea peroxide reaction; Patent CN86104989A discloses a kind of production method of epoxy soybean oil, the method was reacted 7-8 hour with soybean oil, 39% hydrogen peroxide, the vitriol oil, Glacial acetic acid, single stage method sintetics epoxy soybean oil, oxirane value is at 6.0-6.4, and the easy open loop of epoxy group(ing) that this method generates is especially in the epoxidation later stage, because oxidant hydrogen peroxide concentration reduces, epoxidation speed is slower, and the production cycle is long, and temperature of reaction is wayward.The process of above synthesizing epoxy soybean oil all is conventional autoclave rhythmic reaction, aspect temperature control, all adopts the mode that drips, and prevents that temperature from raising very soon, and the oxirane value in reaction later stage is reduced.The reaction of synthetic peroxy acid is again a strong exothermal reaction, if temperature of reaction is too high the danger of blasting is arranged.Therefore for the product iodine number being reduced and can obtaining higher oxirane value, temperature of reaction is control strictly, can not be too high.
At present, the production technique of domestic epoxy soybean oil manufacturer is that the oxirane value of product is between 6-6.5 take " single stage method " solvent-free sulphuric acid catalysis as main.The problem that exists is mainly manifested in: 1. synthesis technique falls behind, and the sour water discharging is large, and temperature control is inaccurate; 2. the side reaction that 4. is difficult to avoid of the low 3. poor stability of equipment and automatic control level causes product quality not high (oxirane value is low).
Summary of the invention
Technical problem to be solved by this invention be for the soybean oil epoxidation can not accurately control temperature of reaction, selectivity is low, security is not high, epoxidation speed is low, can not produce continuously and propose a kind of method for preparing high-quality epoxy soybean oil.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of method for preparing high-quality epoxy soybean oil, aqueous hydrogen peroxide solution and aqueous formic acid are mixed, add again catalyzer and stablizer, again soybean oil and said mixture are pumped in the microchannel module reaction unit, keep reaction time 2 ~ 12min, under 65 ~ 95 ℃, react, reaction product is imported separator, add NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil.
Wherein, described formic acid is replaced with acetic acid.
Wherein, described catalyzer is the vitriol oil or strong phosphoric acid, and the described vitriol oil and strong phosphoric acid concentration are 98wt%; The adding quality of described catalyzer is 1 ~ 15% of soybean oil quality, preferred 2 ~ 15%.
Wherein, described stablizer is urea, EDTA, citric acid, Whitfield's ointment, phosphoric acid, maleic acid, trisodium phosphate or oxine, preferred EDTA, urea or oxine; The adding quality of described stablizer is 1 ~ 25% of soybean oil quality, preferred 2 ~ 23%.
Wherein, the mol ratio of hydrogen peroxide and formic acid (or acetic acid) is 1:1.
Wherein, double key number purpose mol ratio is 2 ~ 18:1 in formic acid (or acetic acid) and the soybean oil, preferred 6 ~ 18:1.
Wherein, described microchannel module reaction unit comprises micro mixer, microstructure heat exchanger, tubulose temperature control modules and the micro-structured reactor that is linked in sequence successively by pipeline, reaction raw materials is realized in input micro mixer and the equipment afterwards thereof by the pump (such as HPLC pump or syringe pump) of accurate and low pulsation, thereby is made material can realize controlling simultaneously its residence time by the microchannel module reaction unit continuously.Can also as required, connect respectively end to end raw material storage tank and product-collecting bottle to realize operate continuously.Described micro mixer is slit plate mixer LH25 (Hastelloy C); The microstructure heat exchanger is coaxial heat exchanger (Hastelloy C); Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixed bed meander reactor HC, preferred sandwich reactor HC.
Wherein, described NaCO
3Aqueous solution mass percentage concentration is 5%.
Wherein, the preferred 2.24 ~ 11.2min of reaction time.Reaction time is the residence time in the micro-structured reactor.
The reaction equation of technique of the present invention is as follows:
Beneficial effect:
The preparation method of epoxy soybean oil provided by the present invention is successive processes, and preparation technology's easy operation control is safe, and reaction conditions is gentle, and reaction time is short, constant product quality, and the epoxidation yield is high.Have production equipment simple, easy to assemble, the characteristics that are easy to carry and move.Can regulate easily by simple increase and decrease microchannel quantity " scale effect " that does not exist similar industrial to produce.
Simultaneously the present invention introduces novel micro-structured reactor, namely raw material in micro-structured reactor, mix, epoxidation, its passage internal diameter is much smaller than the size of popular response device, but its specific surface area can reach 10000-50000m
2/ m
3, the advantage of bringing thus is great heat exchange efficiency and mixing efficiency, can realize the accurate control of temperature of reaction is reached reaction mass with the moment mixing of accurate proportioning.These all are to improve yield, selectivity, security, and the key of quality product.
In view of micro-structured reactor has above advantage, with it for the synthesis of epoxy soybean oil, can overcome the existing problem that exists of producing, improve the transformation efficiency of vegetables oil, Reaction time shorten, the content of reduction by product, the security that greatly improves the epoxy soybean oil production process, improve simultaneously the quality of product, the oxirane value of product＞7.0.
Description of drawings
Fig. 1 is the schematic diagram of microchannel module reaction unit; Wherein, 1 is raw material storage tank; 2 is T-shaped mixing tank; 3 is heat exchanger; 4 is the tubulose temperature control modules; 5 is micro-structured reactor; 6 are product-collecting bottle (cooling off termination reaction with mixture of ice and water).
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described content of embodiment only is used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
The microchannel module reaction unit that following examples were suitable for comprises the raw material storage tank 1, micro mixer 2, microstructure heat exchanger 3, tubulose temperature control modules 4, micro-structured reactor 5 and the product-collecting bottle 6 that are linked in sequence successively by pipeline as shown in Figure 1.Reaction raw materials is realized in input micro mixer and the equipment afterwards thereof by the pump (such as HPLC pump or syringe pump) of accurate and low pulsation, thereby is made material can realize controlling simultaneously its residence time by the microchannel module reaction unit continuously.Polytetrafluoro kapillary by a segment length between micro-structured reactor 5 and the product-collecting bottle 6 connects, and can make it be immersed in ice-water bath with termination reaction.
Described micro mixer is slit plate mixer LH25 (Hastelloy C); Available from Ehrfeld Mikrotechnik BTS GmbH, model is 0109-4-0004-F.
Described microstructure heat exchanger is coaxial heat exchanger (Hastelloy C); Available from Ehrfeld Mikrotechnik BTS GmbH, model is 0309-3-0314-F.
Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixed bed meander reactor HC; Preferred sandwich reactor HC, available from Ehrfeld Mikrotechnik BTS GmbH, model is respectively 0211-2-0314-F; 0213-1-0004-F; 0222-2-2004-F.
The tubulose temperature control modules, available from Ehrfeld Mikrotechnik BTS GmbH, model is 0501-2-1004-F.
Embodiment 1:
Be that 1:1 mixes with the hydrogen peroxide of 30wt% and 98wt% acetic acid according to the mol ratio of hydrogen peroxide and acetic acid, to wherein adding the dense H of catalyzer
2SO
4With stablizer EDTA, the adding quality of catalyzer is 11.26% of soybean oil quality, and it is 17.28% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.5ml/min, 5ml/min, so that double key number purpose mol ratio is 13.5:1 in acetic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.3%.
Embodiment 2:
Be that 1:1 mixes with 30wt% hydrogen peroxide and 98wt% acetic acid according to the mol ratio of hydrogen peroxide and acetic acid, to wherein adding the dense H of catalyzer
3PO
4With stablizer EDTA, the adding quality of catalyzer is 9.0% of soybean oil quality, and it is 13.8% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mol ratio is 10.8:1 in acetic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.07%.
Embodiment 3:
Be that 1:1 mixes with 30wt% hydrogen peroxide and formic acid according to the mol ratio of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer
2SO
4With stablizer EDTA, the adding quality of catalyzer is 11.26% of soybean oil quality, and it is 17.28% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.5ml/min, 5.0ml/min, so that double key number purpose mol ratio is 13.5:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.486%.
Embodiment 4:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes according to the mol ratio of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer
3PO
4With stablizer EDTA, the adding quality of catalyzer is 11.26% of soybean oil quality, and it is 17.28% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.4ml/min, 5.1ml/min, so that double key number purpose mol ratio is 15.8:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.312%.
Embodiment 5:
Be that 1:1 mixes with 30wt% hydrogen peroxide and formic acid according to the mol ratio of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer
2SO
4With stablizer EDTA, the adding quality of catalyzer is 11.26% of soybean oil quality, and it is 17.28% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.4ml/min, 5.1ml/min, so that double key number purpose mol ratio is 15.8:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.582%.
Embodiment 6:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer
2SO
4With stablizer EDTA, the adding quality of catalyzer is 2% of soybean oil quality, and it is 3% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.5ml/min, 5ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.126%.
Embodiment 7:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer
2SO
4With stablizer EDTA, the adding quality of catalyzer is 3% of soybean oil quality, and it is 3% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.2%.
Embodiment 8:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer
2SO
4With stablizer EDTA, the adding quality of catalyzer is 3% of soybean oil quality, and it is 5% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.1%.
Embodiment 9:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer
2SO
4With stablizer EDTA, the adding quality of catalyzer is 3% of soybean oil quality, and it is 6% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.08%.
Embodiment 10:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer
2SO
4With the stablizer urea, the adding quality of catalyzer is 3% of soybean oil quality, and it is 3% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.13%.
Embodiment 11:
With 30wt% hydrogen peroxide and formic acid, be that 1:1 mixes by the mole proportioning of hydrogen peroxide and formic acid, to wherein adding the dense H of catalyzer
2SO
4With the stablizer oxine, the adding quality of catalyzer is 3% of soybean oil quality, and it is 3% of soybean oil quality that stablizer adds quality.The flow velocity of soybean oil and said mixture is controlled at respectively 0.6ml/min, 4.9ml/min, so that double key number purpose mole proportioning is 12:1 in formic acid and the soybean oil, through the microchannel module reaction unit, react in the micro-structured reactor under 75 ℃, reaction time remains on 6.7min.Microchannel module reaction unit back connects the polytetrafluoro kapillary of a segment length, and the polytetrafluoro kapillary is immersed in ice-water bath with termination reaction.Reaction product is imported separator, add 5wt%NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil, and oxirane value is 7.0%.
Embodiment 12:
With the method for embodiment 11, difference is, to wherein adding the dense H of catalyzer
2SO
4With the stablizer citric acid, the adding quality of catalyzer is 1% of soybean oil quality, and it is 1% of soybean oil quality that stablizer adds quality.
Embodiment 13:
With the method for embodiment 11, difference is, to wherein adding the dense H of catalyzer
2SO
4With the stablizer Whitfield's ointment, the adding quality of catalyzer is 15% of soybean oil quality, and it is 25% of soybean oil quality that stablizer adds quality.
Embodiment 14:
With the method for embodiment 11, difference is, to wherein adding the dense H of catalyzer
2SO
4With stablizer phosphoric acid.
Embodiment 15:
With the method for embodiment 11, difference is, to wherein adding the dense H of catalyzer
2SO
4With the stablizer maleic acid.
Embodiment 16:
With the method for embodiment 11, difference is, to wherein adding the dense H of catalyzer
2SO
4With the stablizer trisodium phosphate.
Embodiment 17:
With the method for embodiment 11, difference is that double key number purpose mol ratio is 2:1 in formic acid and the soybean oil.
Embodiment 18:
With the method for embodiment 11, difference is that double key number purpose mol ratio is 18:1 in formic acid and the soybean oil.
Embodiment 19:
With the method for embodiment 11, difference is that reaction time is 2.24min.
Embodiment 20:
With the method for embodiment 11, difference is that reaction time is 11.2min.
Claims (10)
1. method for preparing high-quality epoxy soybean oil, it is characterized in that, aqueous hydrogen peroxide solution and aqueous formic acid are mixed, add again catalyzer and stablizer, again soybean oil and said mixture are pumped in the microchannel module reaction unit, keep reaction time 2 ~ 12min, under 65 ~ 95 ℃, react, reaction product is imported separator, add NaCO
3The aqueous solution, standing demix is removed the aqueous solution of lower floor, and it is 6.5 ~ 7.5 that upper organic phase is washed to the pH value, revolves to steam to dewater, and obtains high-quality epoxy soybean oil.
2. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, described formic acid is replaced with acetic acid.
3. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, described catalyzer is the vitriol oil or strong phosphoric acid; The adding quality of described catalyzer is 1 ~ 15% of soybean oil quality.
4. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, described stablizer is urea, EDTA, citric acid, Whitfield's ointment, phosphoric acid, maleic acid, trisodium phosphate or oxine; The adding quality of described stablizer is 1 ~ 25% of soybean oil quality.
5. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, the mol ratio of hydrogen peroxide and formic acid is 1:1.
6. the method for the high-quality epoxy soybean oil of preparation according to claim 2 is characterized in that, the mol ratio of hydrogen peroxide and acetic acid is 1:1.
7. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, double key number purpose mol ratio is 2 ~ 18:1 in formic acid and the soybean oil.
8. the method for the high-quality epoxy soybean oil of preparation according to claim 2 is characterized in that, double key number purpose mol ratio is 2 ~ 18:1 in acetic acid and the soybean oil.
9. the method for the high-quality epoxy soybean oil of preparation according to claim 1, it is characterized in that, described microchannel module reaction unit comprises micro mixer, microstructure heat exchanger, tubulose temperature control modules and the micro-structured reactor that is linked in sequence successively by pipeline, and reaction raw materials is realized in input micro mixer and the equipment afterwards thereof by the pump of accurate and low pulsation.
10. the method for the high-quality epoxy soybean oil of preparation according to claim 1 is characterized in that, described NaCO
3Aqueous solution mass percentage concentration is 5%.
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| CN103266018A (en) * | 2013-06-17 | 2013-08-28 | 许昌学院 | Preparation method of epoxidized soybean oil |
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| CN103266018B (en) * | 2013-06-17 | 2015-08-19 | 许昌学院 | A kind of preparation method of epoxidised soybean oil |
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