CN116375562A - Refining method for preparing isoborneol by camphene hydration - Google Patents
Refining method for preparing isoborneol by camphene hydration Download PDFInfo
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- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 title claims abstract description 98
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 title claims abstract description 93
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 title claims abstract description 93
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 title claims abstract description 89
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229930006739 camphene Natural products 0.000 title claims abstract description 49
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 31
- 230000036571 hydration Effects 0.000 title claims abstract description 28
- 238000007670 refining Methods 0.000 title claims abstract description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 238000001704 evaporation Methods 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 19
- 239000012046 mixed solvent Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- 238000001953 recrystallisation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 239000006184 cosolvent Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 4
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000013557 residual solvent Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000000746 purification Methods 0.000 description 6
- 241000212314 Foeniculum Species 0.000 description 5
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229940116229 borneol Drugs 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000510672 Cuminum Species 0.000 description 3
- 235000007129 Cuminum cyminum Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000887 hydrating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 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
- WWJLCYHYLZZXBE-UHFFFAOYSA-N 5-chloro-1,3-dihydroindol-2-one Chemical compound ClC1=CC=C2NC(=O)CC2=C1 WWJLCYHYLZZXBE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KGEKLUUHTZCSIP-UHFFFAOYSA-N Isobornyl acetate Natural products C1CC2(C)C(OC(=O)C)CC1C2(C)C KGEKLUUHTZCSIP-UHFFFAOYSA-N 0.000 description 1
- 239000001940 [(1R,4S,6R)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] acetate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 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
- 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
- 239000002304 perfume Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940085790 synthetic camphor Drugs 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a refining method for preparing isoborneol by hydration of camphene, which comprises the steps of evaporating, crystallizing, filtering and drying reaction liquid containing isoborneol after direct hydration to obtain a crude product of isoborneol after removal of camphene, isopropanol and water, dissolving the crude product of isoborneol by using a mixed solvent, and then cooling, recrystallizing, filtering and drying to obtain a qualified isoborneol product.
Description
Technical Field
The invention relates to the technical field of spice purification, in particular to a crystallization and purification method for preparing isoborneol by direct hydration of camphene.
Background
Isoborneol is also known as isotopol, has white semitransparent crystal with special smell, is isomer of Borneolum, and has formula C 10 H 18 O, molecular weight 154.25, melting point 208-214 ℃. Isoborneol is a synthetic camphor and an intermediate of the synthetic borneol, and has wide application in the fields of perfume, medicine and the like.
The preparation method of the isoborneol mainly comprises the following two steps: firstly, synthesizing isobornyl acetate by esterification reaction of camphene and acetic acid, and then hydrolyzing to obtain isoborneol; the second is the direct hydration of camphene in the presence of an acidic catalyst to produce isoborneol. The first indirect method is mature, but has more steps and complex process in the reaction process, and can generate a large amount of wastewater and salt in the subsequent hydrolysis process. The second direct hydration method simplifies the reaction steps, saves raw materials, has simpler process, but has relatively lower conversion rate and selectivity. The choice of suitable reactors, hydration solvents and catalysts is therefore critical to the efficiency of the reaction.
Chinese patent CN101973851A discloses a method for synthesizing isoborneol by using a synthetic molecular sieve as a catalyst, which adopts a fixed bed reactor to react at the reaction temperature of 120-180 ℃, wherein the conversion rate of camphene is 80-90%, and the selectivity of isoborneol is 73.3-86.4%.
The Chinese patent ZL90104209.9 discloses a method for preparing isoborneol by directly hydrating camphene by using dry hydrogen type macroporous strong acid cation exchange resin as a catalyst, wherein a continuous reaction separation circulation reactor is adopted, diacetone alcohol and acetone are used as solvents, after 50 h of reaction temperature is carried out, the conversion rate of camphene is 95.2%, the yield of isoborneol is 73%, and the hydrated camphene is 16.9%; after reaction 80. 80 h, the conversion of camphene was 98.1%, the yield of isoborneol was 85.1%, and the hydrated camphene was 8.8%. The method has the advantages of simple process, high camphene conversion rate and isoborneol yield, low purity of the isoborneol after reaction and high separation difficulty.
The method is characterized in that a separation circulation device is adopted to carry out water and reaction on reactants camphene and water, isopropanol is used as a cosolvent, a crude isoborneol reaction liquid is obtained by a direct hydration method, and impurities such as hydrated camphene, fennel alcohol and the like which are mainly contained in an isoborneol crude product are obtained by hydration, are isomers of the isoborneol, and have close physical and chemical properties, so that how to effectively remove the impurities is a key of industrialization of the isoborneol preparation method by using the camphene direct hydration method.
For separation and purification of fine chemicals, rectification is a common separation means, however, isoborneol has a high melting point, a high boiling point and is easy to sublimate, so that the rectification technology cannot be used. Crystallization is the process of precipitation of solids from a melt, solution or vapor and is widely used in the pharmaceutical industry. Compared with other separation technologies, the crystallization has the advantages of high purity, high selectivity, low energy consumption and the like, which cannot be replaced. CN202011195165.0 discloses a method for purifying natural borneol by recrystallization using ethanol solvent, which has the main disadvantages of low crystallization temperature (-10 ℃ to-30 ℃) and high energy consumption. CN201110099748.8 discloses that the purification of borneol is achieved by recrystallizing borneol twice with acetone solvent. Although isoborneol, cumin and camphene hydrate belong to isomers, their dissolution rates and solubilities in different solvents are different. Therefore, the separation of the isoborneol and the impurities can be realized by adopting a solvent crystallization method, and the aim of purification is fulfilled.
Disclosure of Invention
The method for preparing the isoborneol by directly hydrating the camphene by using the isopropanol as a cosolvent has the characteristics of simple flow and high yield, but the impurities of isomers such as the anisole and the hydrated camphene in the crude isoborneol are difficult to separate and purify. The invention aims to provide a refining method for preparing isoborneol by a hydration method, which takes a reaction solution containing isoborneol crude product obtained by direct hydration as a raw material, obtains the isoborneol crude product after removing camphene, isopropanol and water through evaporation crystallization, filtration and drying, and obtains the high-purity isoborneol by removing isomer impurities through a crystallization purification step by adopting a solvent recrystallization method.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a refining method for preparing isoborneol by camphene hydration comprises the following steps:
(1) Evaporative crystallization
And evaporating the reaction solution containing the isoborneol after direct hydration, and recovering cosolvent isopropanol, water and unreacted camphene required by the hydration method to obtain isoborneol crystal slurry.
Wherein, when the evaporating crystallization is carried out, the evaporating temperature is 85-95 ℃ and the pressure is normal pressure; the reaction solution containing the isoborneol after the raw materials are directly hydrated is deducted from cosolvent isopropanol and water, wherein the content of the isoborneol is 70-80 wt%, camphene is 1-8 wt%, camphene is 5-13 wt% and the content of the cumyl alcohol is 5-12 wt%.
(2) Filtration
And (3) cooling the crude isoborneol crystal slurry obtained after the evaporation and crystallization in the step (1) to room temperature, wherein the cooling rate is 0.5-1.5 ℃/min, and rapidly filtering after cooling.
(3) Drying
And (3) removing residual solvents (mainly cosolvent and water required by hydration reaction) from the filter cake obtained in the step (2) by adopting vacuum drying to obtain the crude isoborneol product.
Wherein the drying temperature is 50-70 ℃, the operating pressure is 5-10 kPa, and the drying is carried out for 2-5 hours;
(4) Solvent recrystallisation
Heating and dissolving the crude isoborneol product by adopting a mixed solvent; then cooling and crystallizing according to a certain cooling rate to form crystallization slurry;
the mixed solvent is a mixed solvent of n-hexane and ethyl acetate, wherein the mass ratio of the n-hexane to the ethyl acetate is 1.5-3: 1, mixing a solvent and a crude product of isoborneol according to a mass ratio of about 0.6-1:1, adding, and starting to heat and dissolve; the dissolution temperature is 60-70 ℃. Activated carbon can be properly added to perform adsorption decolorization according to the color condition of the solution; cooling the solution at a cooling rate of 0.5-0.8 ℃/min, and growing the crystal for 2-3 h when the solution is cooled to 15-20 ℃;
(5) Filtration
And (3) carrying out rapid suction filtration on the slurry obtained after the recrystallization in the step (4).
(6) Drying
And (5) removing residual recrystallization solvent from the filter cake obtained in the step (5) by vacuum drying to obtain the isoborneol product.
Wherein the drying temperature is 50-70 ℃, the operating pressure is 5-10 kPa, and the drying time is 3-5 hours.
The invention has the advantages that:
1. and the characteristics that the camphene, the water and the isopropanol form ternary azeotropy are utilized, and the camphene in the raw materials is removed through evaporation. Under normal pressure operation, the evaporating temperature is 85-95 ℃, isopropanol is extracted, and water and isoborneol are left in the evaporating kettle. The solubility of the isoborneol in water is low, so that the isoborneol can be crystallized and separated out to form solid and liquid, and the solid and liquid separation is realized through filtration, so that the evaporation of water is avoided, and the energy consumption is saved.
The isoborneol is purified by adopting a mixed solvent recrystallization method. The polarity of the solvent is regulated and controlled through the compounding of different solvents, so that the solubility of the isoborneol in the mixed solvent is reduced while the solubility of the hydrated camphene and the fennel alcohol in the mixed solvent at low temperature (15-20 ℃) is ensured, and the problem of low recrystallization yield of the isoborneol in a single solvent is solved. The single pass yield of the isoborneol is higher than 60%. Wherein the solubility of the isoborneol in the solvents of different compounding ratios at 15 ℃ is shown in the following table 1.
TABLE 1 solubility of isoborneol in solvents of different formulation at 15℃
3. The mixed solvent used for recrystallization has low boiling point, small vaporization latent heat, easy realization of recycling of the solvent and low separation energy consumption.
4. The temperature range required by recrystallization is proper (65-15 ℃), the crystallization condition is mild, the low-temperature operation is avoided, and the separation energy consumption is low.
According to the method for refining the isoborneol, the crude isoborneol with the content of about 85wt% is obtained by evaporating and crystallizing the reaction solution obtained by direct hydration, and the crude isoborneol is refined by using the mixed solvent, so that the method is simple to operate and easy to industrialize. The appearance and purity (higher than 95 wt%) of the refined product reach or even exceed the quality of the product synthesized by an indirect method, and the problem that impurities in direct hydration of camphene are difficult to purify is effectively solved.
Drawings
FIG. 1 is a gas chromatogram of crude isoborneol after evaporative crystallization in example 2;
FIG. 2 is a gas chromatogram of the refined isoborneol product of example 2;
FIG. 3 is a scanning electron micrograph of refined isoborneol (flakes) of example 2.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1
1000g of camphene hydration reaction liquid is taken, which comprises 500g of isopropanol, 217g of water, 221g of isoborneol, 14g of camphene, 28g of hydrated camphene and 20g of cumin. The reaction liquid is used as a raw material for evaporation and crystallization, 650g of solution is distilled out, the evaporation of the solution is stopped at 90 ℃, the crystallization slurry is formed at the moment of the evaporation of the solution at the tower bottom, the cooling rate is 1.5 ℃/min, the temperature is reduced to 25 ℃, and the rapid suction filtration is performed. And (3) drying the filter cake in vacuum at the drying temperature of 50 ℃ and the vacuum pressure of 8kPa for 5 hours, and obtaining 250g of crude isoborneol product, wherein the purity of the crude isoborneol product is 85.51%, the hydrated impurity is 8%, the fennel alcohol is 5.5%, and the camphene and other impurities are 1%.
250g of crude isoborneol, 250g of mixed solvent of normal hexane and ethyl acetate, and the mass ratio of the normal hexane to the ethyl acetate in the mixed solvent is 2.5:1, dissolving at 65 ℃, then cooling to 20 ℃ at a cooling rate of 1 ℃/min, and crystallizing and curing for 2 hours. The crystallization slurry is filtered rapidly, and the filter cake is dried in vacuum at 50 ℃ under the vacuum pressure of 8kPa for 5 hours, thus obtaining 151.25g of isoborneol product. The yield of isoborneol was 61.5%. The product is white in color and flaky, and has purity 95.61% as detected by chromatographic analysis, wherein the content of hydrated camphene is less than 3% and the content of fennel alcohol is less than 1%.
Example 2
1000g of camphene hydration reaction liquid is taken, which comprises 500g of isopropanol, 217g of water, 221g of isoborneol, 14g of camphene, 28g of hydrated camphene and 20g of cumin. The reaction liquid is used as a raw material for evaporation and crystallization, 655g of solution is evaporated, the heating of the tower kettle is stopped at 92 ℃, the tower kettle forms crystallization slurry at the moment, the cooling rate is 1.2 ℃/min, the temperature is reduced to 25 ℃, and the rapid filtration is performed. The filter cake is dried in vacuum at 55 ℃ under the vacuum pressure of 8kPa for 4.5 hours, and the crude isoborneol product with the purity of about 252g and the crude isoborneol product with the purity of 84.70 percent is obtained, wherein the hydrated impurity content is less than 9 percent, the content of the cumyl alcohol is about 6 percent, and the content of camphene and other impurities is about 1 percent. The specific contents are shown in table 2 below.
252g of crude isoborneol, 198g of mixed solvent of n-hexane and ethyl acetate, and the mass ratio of n-hexane to ethyl acetate in the mixed solvent is 2.8:1, dissolving at 65 ℃, cooling the solution to 17 ℃ at 0.8 ℃/min, and crystallizing and curing for 2 hours. The crystallization slurry is filtered rapidly, the obtained filter cake is dried in vacuum at the temperature of 50 ℃ and the vacuum pressure of 8kPa for 5 hours, and finally 154.7g of isoborneol product is obtained, and the yield of the isoborneol is 62.4%. The product is white in color and flaky, and has purity of 95.19% as detected by chromatographic analysis, wherein the content of hydrated camphene is below 4% and the content of fennel alcohol is below 1%. The specific contents are shown in table 3 below.
TABLE 2 composition of crude isoborneol product after evaporative crystallization (without solvent propylene glycol monomethyl ether (solvent))
TABLE 3 composition content of the refined isoborneol product (without solvent propylene glycol monomethyl ether (solvent))
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (8)
1. A refining method for preparing isoborneol by camphene hydration is characterized by comprising the following steps:
(1) Evaporative crystallization
Evaporating the reaction solution containing the isoborneol after direct hydration, and recovering cosolvent isopropanol, water and unreacted camphene required by the hydration method to obtain crude isoborneol crystal slurry;
(2) Filtration
Cooling the crude isoborneol crystal slurry obtained after the evaporation and crystallization in the step (1) to room temperature, and then rapidly filtering;
(3) Drying
Vacuum drying the filter cake obtained in the step (2) to remove residual solvent and water to obtain a crude product of the isoborneol;
(4) Solvent recrystallisation
Heating and dissolving the crude isoborneol product by adopting a mixed solvent; then cooling and crystallizing according to a certain cooling rate to form crystallization slurry;
(5) Filtration
Rapidly filtering the slurry obtained after the recrystallization in the step (4);
(6) Drying
And (3) vacuum drying the filter cake obtained in the step (5) to remove residual recrystallization solvent, thereby obtaining the isoborneol product.
2. The refining method for preparing isoborneol by using camphene hydration according to claim 1, which is characterized by comprising the following steps: when the evaporating crystallization is carried out in the step (1), the evaporating temperature is 85-95 ℃ and the pressure is normal pressure.
3. The refining method for preparing isoborneol by using camphene hydration according to claim 1, which is characterized by comprising the following steps: and (3) cooling the crystal slurry formed after the evaporation in the step (2) to room temperature, wherein the cooling rate in the cooling process is 0.5-1.5 ℃/min.
4. The refining method for preparing isoborneol by using camphene hydration according to claim 1, which is characterized by comprising the following steps: in the step (3), the drying temperature is 50-70 ℃, the vacuum condition is 5-10 KPa, and the drying time is 2-5h.
5. The refining method for preparing isoborneol by using camphene hydration according to claim 1, which is characterized by comprising the following steps: in the step (4), the mixed solvent is a mixed solvent of n-hexane and ethyl acetate, wherein the mass ratio of n-hexane to ethyl acetate is 1.5-3: 1, a step of; the mass ratio of the mixed solvent to the crude isoborneol is 0.6-1:1, the dissolution temperature is 60-70 ℃.
6. The refining method for preparing isoborneol by using camphene hydration according to claim 1, which is characterized by comprising the following steps: in the step (4), the cooling rate of the solution is 0.5-0.8 ℃/min, the solution is cooled to 15-20 ℃, and the crystal is grown for 2-3 h.
7. The refining method for preparing isoborneol by using camphene hydration according to claim 1, which is characterized by comprising the following steps: and (3) drying at the temperature of 50-70 ℃ and under the vacuum condition of 5-10 KPa for 3-5h in the step (6).
8. The refining method for preparing isoborneol by using camphene hydration according to claim 1, which is characterized by comprising the following steps: the reaction solution containing the isoborneol after the raw materials are directly hydrated is deducted from cosolvent isopropanol and water, wherein the content of the isoborneol is 70-80 wt%, camphene is 1-8 wt%, camphene is 5-13 wt% and the content of the cumyl alcohol is 5-12 wt%.
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