CN101161615A - A method for preparing Alpha-terpineol by turpentine katalysis-free hydration in near criticality aqueous medium - Google Patents
A method for preparing Alpha-terpineol by turpentine katalysis-free hydration in near criticality aqueous medium Download PDFInfo
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- CN101161615A CN101161615A CNA200710156073XA CN200710156073A CN101161615A CN 101161615 A CN101161615 A CN 101161615A CN A200710156073X A CNA200710156073X A CN A200710156073XA CN 200710156073 A CN200710156073 A CN 200710156073A CN 101161615 A CN101161615 A CN 101161615A
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- terpineol
- alpha
- deionized water
- mixed solvent
- vent valve
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- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 title claims abstract description 62
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229940088601 alpha-terpineol Drugs 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 18
- 230000036571 hydration Effects 0.000 title claims abstract description 15
- 239000012736 aqueous medium Substances 0.000 title claims description 10
- 241000779819 Syncarpia glomulifera Species 0.000 title claims description 9
- 239000001739 pinus spp. Substances 0.000 title claims description 9
- 229940036248 turpentine Drugs 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000047 product Substances 0.000 claims abstract description 51
- 239000008367 deionised water Substances 0.000 claims abstract description 49
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 49
- 239000012046 mixed solvent Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 24
- 238000010792 warming Methods 0.000 claims description 48
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000009835 boiling Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 24
- 238000005194 fractionation Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- -1 add turps then Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000001293 FEMA 3089 Substances 0.000 abstract 3
- 239000003513 alkali Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000004587 chromatography analysis Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 17
- 230000001476 alcoholic effect Effects 0.000 description 12
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- 238000005815 base catalysis Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000005446 dissolved organic matter Substances 0.000 description 3
- NNRLDGQZIVUQTE-UHFFFAOYSA-N gamma-Terpineol Chemical compound CC(C)=C1CCC(C)(O)CC1 NNRLDGQZIVUQTE-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 2
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229930006722 beta-pinene Natural products 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 2
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 241000775848 Syringa oblata Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001877 cajuput oil Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000003205 fragrance Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing alpha-terpineol by catalyzing-free hydration with turpentine oil in subcritical water medium. The procedures of the method are as follows: 1) a high pressure reaction kettle is added with the mixed solvent consisting of the deionized water and the auxiliary solvent, the volume ratio of the deionized water and the auxiliary solvent in the mixed solvent is 1:2 to 8: 1, then the turpentine oil is added, the volume ratio of the mixed solvent and the turpentine oil is 2:1 to 7: 1, then the mixture is stirred, a vent valve is opened for two to five minutes when the temperature rises to boil under normal pressure; 2) the vent valve is closed, the temperature continues to rise between 190 DEG C and 250 DEG C, the reaction is made for 3 to 10 hours; 3) the reaction product is cooled and then is made pressure decreasing and fraction to produce the alpha-terpineol. The invention does not need to add any catalyst during the hydration, solves the pollution problem caused by the acid-alkali catalyzation hydration reaction to the environment, has simple reaction process, higher product yield and better purity, and realizes the innocent treatment of production process.
Description
Technical field
The present invention relates to the method for preparing Alpha-terpineol by turpentine katalysis-free hydration in a kind of near critical aqueous medium.
Background technology
Terpineol 350 has another name called terpinol, is present in cajuput oil, in orange flower oil and the shiu oil etc., its mainly contain α-, β-, γ-three kind of isomer, commercially available Terpineol 350 product is generally three kinds of mixture of isomers, is main composition with alpha-terpineol wherein.
Alpha-terpineol (CAS NO:98-55-5) structural formula:
β-Terpineol 350 (CAS NO:138-87-4) structural formula:
γ-Terpineol 350 (CAS NO:586-81-2) structural formula:
The Terpineol 350 purposes is very extensive.The purified Terpineol 350 contains alcohol amount more than 90%, has Syringa oblata Lindl. fragrance, and is of many uses in perfume industry, be mainly used in soap with and the makeup spices and the essence that is in harmonious proportion.The Terpineol 350 that contains alcohol amount 40%～85% is mainly made defoamer in non-ferro metals floatation industry.In addition, Terpineol 350 also can be applicable to industry such as medicine, purificant, printing ink, instrument, telecommunication.
Natural Terpineol 350 amount is few, can not satisfy industrial needs, therefore mainly produces by synthetic and satisfies industrial needs.China is synthetic Terpineol 350 big producing country, produces nearly 5000 tons per year.Synthetic Terpineol 350 is to be raw material with turps, and the turps main component is α-Pai Xi and beta-pinene, and wherein the content of α-Pai Xi accounts for major part.
α-Pai Xi (CAS NO:7785-20-4) structural formula:
Beta-pinene (CAS NO:127-91-3) structural formula:
Traditional Terpineol 350 synthesis route mainly contains two: (1) two-step approach, and it is to generate hydration card glycol earlier with industrial firpene or turps under the acid catalysis effect, hydration card glycol generates Terpineol 350 with the diluted acid catalytic dehydration again.At present, industrial main employing sulfuric acid two step method is produced, this method exist the production cycle long, consume shortcomings such as height and equipment corrosion be serious.(2) single stage method, it is with industrial firpene or directly generates loose t by alcohol with turps direct hydration under the acid catalysis effect.This method is compared with two-step approach, and flow process has obtained shortening, but environmental problems such as the waste water that production is brought, spent acid still exist.
(Near Critical Water NCW) typically refers to the compressed liquid water of temperature between 250～350 ℃ to near-critical water.Water has following three key properties in this zone:
1) depress at saturated vapo(u)r, the ionization constant of NCW has a maximum value to be about 10 near 275 ℃
-11(mol/kg)
2, its value is 1000 times of normal temperature and pressure water, and ionization constant increases the [H among the NCW with the increase of pressure
3O
+] and [OH
-] concentration is near weak acid or weak base, self has the function of acid catalysis and base catalysis, therefore can make some acid-base catalyzed reaction needn't add acid base catalysator, thereby avoid the neutralization of soda acid, the operations such as processing of salt;
2) depress at saturated vapo(u)r, the specific inductivity of 20 ℃ of water is 80.1, and has only 23.5 275 ℃ the time.Although the specific inductivity of NCW is still bigger, solubilized even ionized salts, enough little of dissolved organic matter, (275 ℃ of saturated vapo(u)rs density of depressing water is 0.76g/cm to add that the density of NCW is big
3, the specific inductivity of NCW, density and acetone are close), so NCW has extraordinary solubility property, has the characteristic of dissolved organic matter and inorganics simultaneously.This can carry out the building-up reactions in many NCW media in homogeneous phase, thereby eliminates resistance to mass transfer, improves speed of response, and the reaction back only needs simple cooling just can realize oily water separation simultaneously, and water can be recycled;
3) physicochemical property such as the specific inductivity of NCW, ion-product constant, density, viscosity, spread coefficient, solubleness are adjustable continuously in the scope of broad with temperature, pressure, the rerum natura that is NCW has controllability (tuning property), therefore as reaction medium, NCW has different solvent properties and reactivity worth at different states.
The applied research of reacting among the NCW comprises that offal treatment, macromolecular material recycle, inorganic materials are synthetic, gelatin liquefaction and biomass as resources etc., to going deep into that these three characteristics are familiar with, make the Application Areas among the NCW constantly obtain enlarging just because of people.
The present invention is applied to near-critical water to utilize the characteristic of near-critical water on the terebinthine hydration reaction as reaction medium, realizes preparing from the no catalysis of turps, efficiently, greenly alpha-terpineol.
Summary of the invention
The purpose of this invention is to provide a kind of from the no catalysis of turps, efficient, the green method for preparing alpha-terpineol.
The step of method is as follows:
1) adds the mixed solvent of forming by deionized water and solubility promoter in the autoclave, the volume ratio of deionized water and solubility promoter is 1: 2～8: 1 in the mixed solvent, add turps then, mixed solvent and turps volume ratio are 2: 1～7: 1, open stirring, be warming up to boiling under the normal pressure, opened vent valve 2～5 minutes;
2) close vent valve, continue to be warming up to 190～250 ℃, reaction 3～10h;
3) carry out vacuum fractionation after the reaction product cooling, obtain the alpha-terpineol product.
The purpose that " is warming up to boiling under the normal pressure, opened vent valve 2～5 minutes " in the step 1) of the present invention is to utilize water vapour to take away the interior oxygen of still, to reduce the generation of side reaction, improves the yield of product.
Step 2) the system reaction pressure is the saturation vapour pressure of mixed solvent under this temperature in.
The solvent that vacuum fractionation obtains in the step 3) can be recycled.
The present invention need not add any catalyzer in reaction process, self acid-base catalysis characteristic of utilizing near-critical water makes turps no catalytic hydration generation alpha-terpineol near critical aqueous medium with characteristic that can dissolved organic matter, solved an acid-base catalysis hydration reaction pollution on the environment difficult problem, reaction process is simple, product yield is higher, purity is better, and has realized the greenization of production process.
Description of drawings
Accompanying drawing is the process flow diagram of preparing Alpha-terpineol by turpentine katalysis-free hydration in the near critical aqueous medium.
Embodiment
The alpha-terpineol product adopts gas chromatographic analysis, and chromatographic condition is: chromatographic column is 30m * 0.32mm * 0.4 μ m SE-54 (low-pole); Hydrogen flame ionization detector (FID); Injector temperature: 250 ℃; Detector temperature: 250 ℃; Column temperature adopts the temperature programming method, and heating schedule is: 110 ℃ (5min), 5 ℃/min are warming up to 160 ℃; N
2Press before the post: 60kPa; H
2Press before the post: 80kPa; Sample size: 2 μ l; Calculate the mass content of alpha-terpineol in the product by area normalization method.
Embodiment 1
Add the mixed solvent 300mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 1: 1, then add 150mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 2 minutes; Close vent valve, continue to be warming up to 200 ℃ of reactions 9 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 29.2g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 80.5% in the product.
Embodiment 2
Add the mixed solvent 300mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 2: 1, then add 100mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 3 minutes; Close vent valve, continue to be warming up to 190 ℃ of reactions 9 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 19.2g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 81.2% in the product.
Embodiment 3
Add the mixed solvent 300mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 1: 1, then add 100mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 4 minutes; Close vent valve, continue to be warming up to 200 ℃ of reactions 8 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 23.9g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 82.1% in the product.
Embodiment 4
Add the mixed solvent 300mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 1: 2, then add 100mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 5 minutes; Close vent valve, continue to be warming up to 210 ℃ of reactions 8 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 22.8g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 81.8% in the product.
Embodiment 5
Add the mixed solvent 300mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 3: 1, then add 100mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 2 minutes; Close vent valve, continue to be warming up to 220 ℃ of reactions 6 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 20.9g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 81.2% in the product.
Embodiment 6
Add the mixed solvent 300mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 4: 1, then add 100mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 3 minutes; Close vent valve, continue to be warming up to 230 ℃ of reactions 5 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 17.6g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 80.9% in the product.
Embodiment 7
Add the mixed solvent 300mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 6: 1, then add 100mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 4 minutes; Close vent valve, continue to be warming up to 240 ℃ of reactions 4 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 15.7g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 80.2% in the product.
Embodiment 8
Add the mixed solvent 300mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 8: 1, then add 100mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 5 minutes; Close vent valve, continue to be warming up to 250 ℃ of reactions 3 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 10.6g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 80.1% in the product.
Embodiment 9
Add the mixed solvent 320mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 1: 1, then add 80mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 2 minutes; Close vent valve, continue to be warming up to 200 ℃ of reactions 7 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 18.2g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 82.3% in the product.
Embodiment 10
Add the mixed solvent 350mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 1: 1, then add 70mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 3 minutes; Close vent valve, continue to be warming up to 200 ℃ of reactions 6 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 14.9g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 82.8% in the product.
Embodiment 11
Add the mixed solvent 360mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 1: 1, then add 60mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 4 minutes; Close vent valve, continue to be warming up to 200 ℃ of reactions 5 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 10.7g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 81.3% in the product.
Embodiment 12
Add the mixed solvent 350mL that deionized water and ethanol are formed in the 500mL autoclave, wherein deionized water and alcoholic acid volume ratio are 1: 1, then add 50mL turps, open stirring, are warming up to boiling under the normal pressure, open vent valve 5 minutes; Close vent valve, continue to be warming up to 200 ℃ of reactions 4 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 8.4g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 80.8% in the product.
Embodiment 13
Add the mixed solvent 300mL that deionized water and acetone are formed in the 500mL autoclave, wherein the volume ratio of deionized water and acetone is 1: 1, then adds 100mL turps, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2 minutes; Close vent valve, continue to be warming up to 200 ℃ of reactions 7.5 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 23.6g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 82.3% in the product.
Embodiment 14
Add the mixed solvent 300mL that deionized water and acetone are formed in the 500mL autoclave, wherein the volume ratio of deionized water and acetone is 2: 1, then adds 100mL turps, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 3 minutes; Close vent valve, continue to be warming up to 210 ℃ of reactions 6.5 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 22.7g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 82.1% in the product.
Embodiment 15
Add the mixed solvent 300mL that deionized water and acetone are formed in the 500mL autoclave, wherein the volume ratio of deionized water and acetone is 3: 1, then adds 100mL turps, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 4 minutes; Close vent valve, continue to be warming up to 220 ℃ of reactions 5.5 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 20.7g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 81.8% in the product.
Embodiment 16
Add the mixed solvent 300mL that deionized water and tetrahydrofuran (THF) are formed in the 500mL autoclave, wherein the volume ratio of deionized water and tetrahydrofuran (THF) is 1: 1, then adds 100mL turps, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 5 minutes; Close vent valve, continue to be warming up to 200 ℃ of reactions 9 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 24.6g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 82.5% in the product.
Embodiment 17
Add the mixed solvent 300mL that deionized water and tetrahydrofuran (THF) are formed in the 500mL autoclave, wherein the volume ratio of deionized water and tetrahydrofuran (THF) is 2: 1, then adds 100mL turps, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2 minutes; Close vent valve, continue to be warming up to 210 ℃ of reactions 8 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 24.2g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 82.3% in the product.
Embodiment 18
Add the mixed solvent 300mL that deionized water and tetrahydrofuran (THF) are formed in the 500mL autoclave, wherein the volume ratio of deionized water and tetrahydrofuran (THF) is 3: 1, then adds 100mL turps, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 3 minutes; Close vent valve, continue to be warming up to 220 ℃ of reactions 7 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 22.7g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 81.8% in the product.
Embodiment 19
Add the mixed solvent 300mL that deionized water and Virahol are formed in the 500mL autoclave, wherein the volume ratio of deionized water and tetrahydrofuran (THF) is 1: 1, then adds 100mL turps, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 4 minutes; Close vent valve, continue to be warming up to 200 ℃ of reactions 10 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 25.6g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 82.3% in the product.
Embodiment 20
Add the mixed solvent 300mL that deionized water and Virahol are formed in the 500mL autoclave, wherein the volume ratio of deionized water and tetrahydrofuran (THF) is 2: 1, then adds 100mL turps, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 5 minutes; Close vent valve, continue to be warming up to 210 ℃ of reactions 9 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 24.5g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 81.7% in the product.
Embodiment 21
Add the mixed solvent 300mL that deionized water and Virahol are formed in the 500mL autoclave, wherein the volume ratio of deionized water and tetrahydrofuran (THF) is 3: 1, then adds 100mL turps, opens stirring, is warming up to boiling under the normal pressure, opens vent valve 2 minutes; Close vent valve, continue to be warming up to 220 ℃ of reactions 8 hours; Carry out vacuum fractionation after the reaction product cooling, obtain alpha-terpineol product 23.5g.Through gas chromatographic analysis, the mass content of alpha-terpineol is 80.9% in the product.
Claims (5)
1. the method for preparing Alpha-terpineol by turpentine katalysis-free hydration in the near critical aqueous medium is characterized in that the step of method is as follows:
1) adds the mixed solvent of forming by deionized water and solubility promoter in the autoclave, the volume ratio of deionized water and solubility promoter is 1: 2～8: 1 in the mixed solvent, add turps then, mixed solvent and turps volume ratio are 2: 1～7: 1, open stirring, be warming up to boiling under the normal pressure, opened vent valve 2～5 minutes;
2) close vent valve, continue to be warming up to 190～250 ℃, reaction 3～10h;
3) carry out vacuum fractionation after the reaction product cooling, obtain the alpha-terpineol product.
2. the method for preparing Alpha-terpineol by turpentine katalysis-free hydration in a kind of near critical aqueous medium according to claim 1 is characterized in that the volume ratio of deionized water and solubility promoter is 1: 1～3: 1 in the mixed solvent described in the step 1).
3. the method for preparing Alpha-terpineol by turpentine katalysis-free hydration in a kind of near critical aqueous medium according to claim 1 is characterized in that mixed solvent described in the step 1) and turps volume ratio are 3: 1～5: 1.
4. the method for preparing Alpha-terpineol by turpentine katalysis-free hydration in a kind of near critical aqueous medium according to claim 1 is characterized in that the solubility promoter described in the step 1) is Virahol, tetrahydrofuran (THF), acetone or ethanol.
5. the method for preparing Alpha-terpineol by turpentine katalysis-free hydration is characterized in that step 2 in a kind of near critical aqueous medium according to claim 1) described in temperature of reaction be 200～220 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557877A (en) * | 2012-01-06 | 2012-07-11 | 长沙理工大学 | Method for increasing yield of terpinol in near homogenous phase double-phase reaction system |
| CN107628927A (en) * | 2017-09-28 | 2018-01-26 | 云南森美达生物科技有限公司 | The method that hesperidene synthesizes a terpinols |
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2007
- 2007-10-11 CN CN200710156073A patent/CN100586914C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557877A (en) * | 2012-01-06 | 2012-07-11 | 长沙理工大学 | Method for increasing yield of terpinol in near homogenous phase double-phase reaction system |
| CN107628927A (en) * | 2017-09-28 | 2018-01-26 | 云南森美达生物科技有限公司 | The method that hesperidene synthesizes a terpinols |
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| CN100586914C (en) | 2010-02-03 |
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