CN108503520A - A kind of technique of reactive distillation synthesis menthones - Google Patents
A kind of technique of reactive distillation synthesis menthones Download PDFInfo
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- CN108503520A CN108503520A CN201810494551.6A CN201810494551A CN108503520A CN 108503520 A CN108503520 A CN 108503520A CN 201810494551 A CN201810494551 A CN 201810494551A CN 108503520 A CN108503520 A CN 108503520A
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- menthones
- catalyst
- ruthenium
- reactive distillation
- technique
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- 150000002729 menthone derivatives Chemical class 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000000066 reactive distillation Methods 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 title claims description 12
- 238000003786 synthesis reaction Methods 0.000 title claims description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 7
- 230000005012 migration Effects 0.000 claims abstract description 7
- 238000013508 migration Methods 0.000 claims abstract description 7
- ZYTMANIQRDEHIO-KXUCPTDWSA-N isopulegol Chemical compound C[C@@H]1CC[C@@H](C(C)=C)[C@H](O)C1 ZYTMANIQRDEHIO-KXUCPTDWSA-N 0.000 claims description 38
- 229910052707 ruthenium Inorganic materials 0.000 claims description 31
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 30
- 239000001871 (1R,2R,5S)-5-methyl-2-prop-1-en-2-ylcyclohexan-1-ol Substances 0.000 claims description 19
- 229940095045 isopulegol Drugs 0.000 claims description 19
- ZYTMANIQRDEHIO-UHFFFAOYSA-N neo-Isopulegol Natural products CC1CCC(C(C)=C)C(O)C1 ZYTMANIQRDEHIO-UHFFFAOYSA-N 0.000 claims description 19
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002815 homogeneous catalyst Substances 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000012495 reaction gas Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000011946 reduction process Methods 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 240000002853 Nelumbo nucifera Species 0.000 claims description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 3
- 235000006510 Nelumbo pentapetala Nutrition 0.000 claims description 3
- KDUIUFJBNGTBMD-VXMYFEMYSA-N cyclooctatetraene Chemical compound C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- HWNXEHYDQGFUNE-UHFFFAOYSA-N [Na].Cl.[Ru] Chemical compound [Na].Cl.[Ru] HWNXEHYDQGFUNE-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 claims description 2
- 229930007927 cymene Natural products 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 125000002872 norbornadienyl group Chemical group C12=C(C=C(CC1)C2)* 0.000 claims description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 2
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 3
- 239000000852 hydrogen donor Substances 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000003205 fragrance Substances 0.000 description 5
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 4
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 244000246386 Mentha pulegium Species 0.000 description 4
- 235000016257 Mentha pulegium Nutrition 0.000 description 4
- 235000004357 Mentha x piperita Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 235000001050 hortel pimenta Nutrition 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229940041616 menthol Drugs 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 4
- NFLGAXVYCFJBMK-UHFFFAOYSA-N Menthone Chemical compound CC(C)C1CCC(C)CC1=O NFLGAXVYCFJBMK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NFLGAXVYCFJBMK-IUCAKERBSA-N (-)-isomenthone Chemical compound CC(C)[C@@H]1CC[C@H](C)CC1=O NFLGAXVYCFJBMK-IUCAKERBSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 244000272264 Saussurea lappa Species 0.000 description 2
- 235000006784 Saussurea lappa Nutrition 0.000 description 2
- 239000005844 Thymol Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 229960000790 thymol Drugs 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NFLGAXVYCFJBMK-RKDXNWHRSA-N (+)-isomenthone Natural products CC(C)[C@H]1CC[C@@H](C)CC1=O NFLGAXVYCFJBMK-RKDXNWHRSA-N 0.000 description 1
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Camphene hydrate Chemical compound C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229930007503 menthone Natural products 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- LMTWGVRWCWNOAC-UHFFFAOYSA-N phenol;ruthenium Chemical compound [Ru].OC1=CC=CC=C1 LMTWGVRWCWNOAC-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the techniques that a kind of reactive distillation synthesizes menthones, using reactive distillation column as consersion unit, under mild reaction conditions and under the action of catalyst and auxiliary agent, asymmetric catalytic hydrogenation is realized by the hydrogen migration of molecule itself, avoid the use of hydrogen or its hydrogen donor and oxidant, product can be continuously produced simultaneously, there is significant continuous operability and economy, there is preferable industrial prospect.
Description
Technical field
The invention belongs to the techniques that field of fine chemical more particularly to a kind of reactive distillation synthesize menthones.
Background technology
Menthones (Menthone), molecular formula：C10H18O, alias Meng's ketone are dissolved in 3 volume, 70% ethyl alcohol, are dissolved in oil
Matter fragrance.Molecular weight 154.25.Density 0.896g/cm3.205 DEG C of boiling point.Refractive index 1.450.It is slightly soluble in water.It is dissolved in most of
Organic solvent.With 1:3 are dissolved in 70% ethyl alcohol, are dissolved in oily fragrance.There are refrigerant peppermint sample fragrance, root of Aucklandia lappa Decne inside information.Fragrance dissipates
Hair, not very persistently, taste is refrigerant, but also has offending bitter taste.There are refrigerant peppermint sample fragrance, root of Aucklandia lappa Decne inside information.
Menthones, alias Meng's ketone, the refrigerant characteristic perfume with natural peppermint.Menthones is with two kinds of stereoisomers
Form exists：Menthones and isomenthone respectively exist in the form of two kinds of enantiomters again, mainly thin to prepare
Lotus type essence, therefore the synthesis of menthones is constantly subjected to the concern of people.
Patent US3124614 reports, which are hydrogenated using thymol under Pd catalyst actions, can obtain menthones, but raw material
Thymol is difficult to obtain, severe reaction conditions, to equipment requirement height.
Patent CN106061933A reports the isopulegol in gas phase and is contacted with activated oxidisability copper catalyst
The method for preparing menthones, copper catalyst need to carry out pre-activate in this method, and pre-activation method is cumbersome, and activation effect is to reaction
Yield is affected, and is not suitable for large-scale industrial production.
Patent CN104603095A uses the metal complex for containing Phosphine ligands as catalyst.The technique can reach
85% or more menthones yield, but high turnover number (TON) is cannot achieve, catalyst life is shorter, it is contemplated that the height of catalyst
Cost, this technique are not suitable for industry and are combined to menthones.
Ruthenium-phenol catalyst of the patent CN106068160A descriptions for transfer hydrogenation, and the catalyst is shifting
There is excellent performance in hydrogenation, be used for the catalyst to prepare menthones by isopulegol, there is higher conversion
Rate and selectivity.But the turnover number of the technique (TON) raising is limited, catalyst life is still shorter, but also needs to use
A large amount of amphyl, this will produce adverse effect for post-processing and environment.
Therefore, urgent need is a kind of simple for process, and reaction condition is mild, and economical and efficient, environmental protection is friendly and is easily industrialized
Method realize the preparation of menthones.
Invention content
The purpose of the present invention is to provide a kind of method that reactive distillation prepares menthones, to solve it is existing prepare it is thin
Problems present in lotus ketone technique, the present invention are under mild reaction conditions, high using heterogeneous catalysis isopulegol
Yield prepares menthones, easily mode can recycle catalyst, have simpler reaction process, it is lower reaction at
This, good environment friendly has preferable industrial prospect.If do not made separate stipulations, term " menthones " refers to appointing
What possible stereoisomer.
A kind of technique of reactive distillation synthesis menthones, which is characterized in that include the following steps：
(1) isopulegol is entered in preheater, is heated to 80-90 DEG C；
(2) isopulegol after preheating is imported with auxiliary agent in reactive distillation column, vacuum degree control is -0.1 in tower
~-0.15Mpa, reboiler temperature are controlled at 120-130 DEG C, and catalyst of the menthones with filler layer surface on column plate is allowed to fill
Tap touches the hydrogen migration realization asymmetric catalytic hydrogenation for carrying out molecule itself, using 4-5:1 reflux ratio carries out rectifying；When carrying
Take out after menthones materials and parts quality meets product requirement, into cooler in it is cooling, be normal temperature circulation water in cooler, finally
Into finished product storage tank, finished product menthones is obtained.
The tower height of the reactive distillation rectifying column is 20-25 meters, tower diameter DN250-300, and filler is stainless steel ripple silk net
And catalyst.
The catalyst is a kind of supported ruthenium catalyst Ru/CNTS, in terms of the gross mass of catalyst, the weight content of Ru
It is 5~10%,
Further, the preparation method of the Ru/CNTS catalyst includes the following steps：
1) carbon nanotube that a certain amount of outer diameter is 2~6nm is weighed, the HNO that mass fraction is 30%~50% is added3
The H that solution and 20~50ml mass fractions are 15%2O2Solution is heated to reflux 2~3h, after taking-up under the conditions of 100~120 DEG C
It is cooled to room temperature, washs, filters by conventional method, is dry, obtaining the modified carbon nanotube in surface.
2) reduction process is impregnated, carbon nano-tube material modified is crushed, it is small with ruthenium saline solution dipping 12~24
When, then restored with reducing agent, it is washed with deionized to neutrality, then be dried, obtains ruthenium catalyst；
3) ruthenium catalyst roasting process roasts ruthenium catalyst, the ruthenium-based catalyst aoxidized；
4) ruthenium-based catalyst by the oxidation that step 3) obtains is added in reaction kettle, is passed through hydrogen displacement reaction gas,
Hydrogenation activation is carried out, reaction temperature is 10~40 DEG C, and preferably 20~30 DEG C, it is 0~1.0MPaG to maintain reaction gauge pressure, preferably
0.1~0.5MPaG, the reaction time be 6~for 24 hours, preferably 8~12h.
Preferably, in the step 2), the ruthenium salt is set as ruthenium trichloride or ruthenium hydrochloride sodium or carbonyl chlorination
Ruthenium, the ruthenium salinity are 5~15g/L.
Preferably, in the step 2), the reducing agent is set as one in hydrazine hydrate, potassium borohydride, formaldehyde
Kind.
Preferably, in the step 3), calcination temperature is set as 200~600 DEG C, and roasting time is set as 3~5
Hour.
In the present invention, the auxiliary agent is selected from norbornadiene, cyclopentene, cyclopentadiene, pentamethylcyclopentadiene, ethyl
It is one or more in cyclopentadiene, cyclo-octene, cyclo-octadiene, cyclo-octatetraene, cycloheptene, cymene, preferred cyclopentadiene
And/or cyclo-octadiene.
It reacts in finally obtained product, the ratio of isomenthone is 10-20mol%, preferably 10mol%.
It in the present invention, is calculated with the amount of the substance of isopulegol, oil ratio is 0.0001%~l%, preferably
0.001%~0.1%；The molar ratio of the auxiliary agent and homogeneous catalyst dosage is (0.01~10)：1, preferably (0.1~4)：
1。
Preferably, reaction final product chemo-selective is 95%~99%, and conversion ratio can reach 90%~99.9%.
The advantageous effect of the method for the present invention is：
1) it under mild reaction conditions under the action of catalyst and auxiliary agent, is realized by the hydrogen migration of molecule itself
Asymmetric catalytic hydrogenation avoids the use of hydrogen or its hydrogen donor and oxidant, while can be continuous using reactive distillation column
Product is produced, there is significant continuous operability and economy；Secondly, it is not related to other solvents in system, reduces it
The introducing of his impurity has good environment friendly.
2) auxiliary agent through the invention, it is possible to reduce the loss of transition metal in reaction process, hence it is evident that improve catalyst system and catalyzing
Stability；System does not add solvent, further simplifies the later purification processing of reaction product, and the three wastes significantly reduce, have
Preferable industrial prospect.
Specific implementation mode
Below in conjunction with technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described
Embodiment be only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, originally
The every other embodiment that domain those of ordinary skill is obtained without making creative work is added in neck, all belongs to
In the scope of protection of the invention.
【Embodiment 1】
1) carbon nanotube that a certain amount of outer diameter is 2nm is weighed, the HNO that mass fraction is 35% is added3Solution and 20ml
The H that mass fraction is 15%2O2Solution is heated to reflux 2~3h under the conditions of 100 DEG C, takes out postcooling to room temperature, passes through routine
Method washing filters, is dry, obtains the modified carbon nanotube in surface；
2) reduction process is impregnated, carbon nano-tube material modified is crushed, it is water-soluble with a concentration of 5g/L ruthenium trichlorides
Liquid impregnates 12 hours, then is restored with reducing agent hydrazine hydrate, potassium borohydride, formaldehyde, is washed with deionized to neutrality, then carry out
It is dry, obtain ruthenium catalyst；
3) ruthenium catalyst roasting process roasts ruthenium catalyst, and calcination temperature is 500 DEG C, and roasting time is 3~5
Hour, obtain the ruthenium-based catalyst of ruthenium surface oxidation；
4) ruthenium-based catalyst by the oxidation that step 3) obtains is added in reaction kettle, is passed through hydrogen displacement reaction gas,
Carry out hydrogenation activation, reaction temperature is 20 DEG C, and it is 0~1.0MPaG to maintain reaction gauge pressure, preferably 0.2MPaG, and the reaction time is
12h obtains the Ru/CNTS catalyst that Ru contents are 5.1%.
【Embodiment 2】
1) carbon nanotube that a certain amount of outer diameter is 2nm is weighed, the HNO that mass fraction is 35% is added3Solution and 20ml
The H that mass fraction is 15%2O2Solution is heated to reflux 2~3h under the conditions of 100 DEG C, takes out postcooling to room temperature, passes through routine
Method washing filters, is dry, obtains the modified carbon nanotube in surface；
2) reduction process is impregnated, carbon nano-tube material modified is crushed, with a concentration of 10g/L ruthenium trichlorides water
Solution impregnates 18 hours, then with reducing agent potassium borohydride reduction, is washed with deionized to neutrality, then be dried, obtains ruthenium
Catalyst；
3) ruthenium catalyst roasting process roasts ruthenium catalyst, and roasting is set as 600 DEG C, and calcination temperature is set as
5 hours, obtain the ruthenium-based catalyst of ruthenium surface oxidation；
4) ruthenium-based catalyst by the oxidation that step 3) obtains is added in reaction kettle, is passed through hydrogen displacement reaction gas,
Hydrogenation activation is carried out, reaction temperature is 30 DEG C, and it is 0.5MPaG, reaction time 6h to maintain reaction gauge pressure, and obtaining Ru contents is
8.7% Ru/CNTS catalyst.
【Embodiment 3】
Catalyze and synthesize menthones：
A kind of method that reactive distillation prepares menthones：
(1) isopulegol is entered in preheater, is heated to 80 DEG C；
(2) isopulegol after preheating is imported with auxiliary agent norbornadiene and cyclo-octadiene in reactive distillation column, tower
In -0.15Mpa, reboiler temperature is controlled at 120 DEG C interior vacuum degree control, allow menthones on column plate with filler layer surface
Catalyst comes into full contact with the hydrogen migration realization asymmetric catalytic hydrogenation for carrying out molecule itself, using 4:1 reflux ratio carries out essence
It evaporates；After extracting menthones materials and parts quality and meeting product requirement, into cooler in it is cooling, be normal temperature circulation in cooler
Water finally enters finished product storage tank, obtains finished product menthones.
It is calculated with the amount of the substance of isopulegol, oil ratio 0.1%；The auxiliary agent and homogeneous catalyst dosage
Molar ratio is 4：1.
The tower height of the reactive distillation rectifying column is 20 meters, tower diameter DN250, and filler is stainless steel ripple silk net and catalysis
Agent；The catalyst is the Ru/CNTS catalyst that the Ru contents prepared by embodiment 1 are 5.1%.
Conversion ratio and menthol yield are measured by calibrating GC analyses, the results are shown in Table 1.
【Embodiment 4】
Catalyze and synthesize menthones：
A kind of method that reactive distillation prepares menthones：
(1) isopulegol is entered in preheater, is heated to 90 DEG C；
(2) isopulegol after preheating is imported with auxiliary agent cyclopentadiene and cyclo-octatetraene in reactive distillation column, in tower
In -0.1Mpa, reboiler temperature is controlled at 130 DEG C vacuum degree control, allows catalysis of the menthones with filler layer surface on column plate
Agent comes into full contact with the hydrogen migration realization asymmetric catalytic hydrogenation for carrying out molecule itself, using 5:1 reflux ratio carries out rectifying；When
Extract after menthones materials and parts quality meets product requirement, into cooler in it is cooling, be normal temperature circulation water in cooler, most
Enter finished product storage tank afterwards, obtains finished product menthones.
It is calculated with the amount of the substance of isopulegol, oil ratio 0.01%；The auxiliary agent and homogeneous catalyst dosage
Molar ratio is 0.1：1.
The tower height of the reactive distillation rectifying column is 25 meters, tower diameter DN300, and filler is stainless steel ripple silk net and catalysis
Agent；The catalyst is the Ru/CNTS catalyst that the Ru contents prepared by embodiment 7 are 8.7%.
Conversion ratio and menthol yield are measured by calibrating GC analyses, the results are shown in Table 1.
【Embodiment 4】
Catalyze and synthesize menthones：
A kind of method that reactive distillation prepares menthones：
(1) isopulegol is entered in preheater, is heated to 90 DEG C；
(2) isopulegol after preheating is imported with auxiliary agent cyclopentadiene in reactive distillation column, vacuum degree control in tower
In -0.1Mpa, reboiler temperature is controlled at 130 DEG C, and catalyst of the menthones with filler layer surface on column plate is allowed to come into full contact with
Asymmetric catalytic hydrogenation is realized in the hydrogen migration for carrying out molecule itself, using 5:1 reflux ratio carries out rectifying；When extracting peppermint
After ketone materials and parts quality meets product requirement, into cooler in it is cooling, be normal temperature circulation water in cooler, finally enter finished product
Storage tank obtains finished product menthones.
It is calculated with the amount of the substance of isopulegol, oil ratio 0.01%；The auxiliary agent and homogeneous catalyst dosage
Molar ratio is 0.1：1.
The tower height of the reactive distillation rectifying column is 25 meters, tower diameter DN300, and filler is stainless steel ripple silk net and catalysis
Agent；The catalyst is the Ru/CNTS catalyst that the Ru contents prepared by embodiment 7 are 8.7%.
Conversion ratio and menthol yield are measured by calibrating GC analyses, the results are shown in Table 1.
【Comparative example 1】
Catalyze and synthesize menthones.
Palladium-the ruthenium catalyst and isopulegol that are prepared in embodiment 1 are all put into dry 500ml reaction under high pressures
In kettle, it is 4Mpa to be passed through high pure nitrogen and maintain reaction absolute pressure, which is heated to 130 DEG C and is stirred 50 hours.Pass through school
Quasi- GC analyses measure conversion ratio and menthol yield, as a result as shown in table 1.
Table 1
Above description has fully disclosed the specific implementation mode of the present invention.It should be pointed out that being familiar with the field
Technical staff is to any change for being done of specific implementation mode of the present invention all without departing from the model of claims of the present invention
It encloses.Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (9)
1. a kind of technique of reactive distillation synthesis menthones, which is characterized in that include the following steps：
(1) isopulegol is entered in preheater, is heated to 80-90 DEG C；
(2) isopulegol and the auxiliary agent after preheating are imported in reactive distillation column, in tower vacuum degree control -0.1~-
0.15Mpa, reboiler temperature are controlled at 120-130 DEG C, and menthones is allowed fully to be connect with the catalyst of filler layer surface on column plate
The hydrogen migration realization asymmetric catalytic hydrogenation for carrying out molecule itself is touched, using 4-5:1 reflux ratio carries out rectifying；It is thin when extracting
After lotus ketone materials and parts quality meets product requirement, into cooler in it is cooling, be normal temperature circulation water in cooler, finally enter finished product
Storage tank obtains finished product menthones；The catalyst is a kind of supported ruthenium catalyst Ru/CNTS.
2. the technique of reactive distillation synthesis menthones according to claim 1, it is characterised in that：The reactive distillation rectifying
The tower height of tower is 20-25 meters, tower diameter DN250-300, and filler is stainless steel ripple silk net and catalyst.
3. the technique of reactive distillation synthesis menthones according to claim 1, it is characterised in that：The Ru/CNTS catalysis
Agent, in terms of the gross mass of catalyst, the weight content of Ru is 5~10%；
It is pungent that the auxiliary agent is selected from norbornadiene, cyclopentene, cyclopentadiene, pentamethylcyclopentadiene, ethyl cyclopentadiene, ring
It is one or more in alkene, cyclo-octadiene, cyclo-octatetraene, cycloheptene, cymene, preferably cyclopentadiene and/or cyclo-octadiene.
4. the technique of reactive distillation synthesis menthones according to claim 1, it is characterised in that：With the object of isopulegol
The amount of matter calculates, and oil ratio is 0.0001%~l%, and preferably 0.001%~0.1%；The auxiliary agent and homogeneous catalyst dosage
Molar ratio be (0.01~10)：1, preferably (0.1~4)：1.
5. the technique of reactive distillation synthesis menthones according to claim 1, it is characterised in that：React final product chemistry
Selectivity is 95%~99%, and conversion ratio can reach 90%~99.9%.
6. the technique for synthesizing menthones according to claim 1-5 any one of them reactive distillations, it is characterised in that：The Ru/
The preparation method of CNTS catalyst includes the following steps：
1) carbon nanotube that a certain amount of outer diameter is 2~6nm is weighed, the HNO that mass fraction is 30%~50% is added3Solution and
The H that 20~50ml mass fractions are 15%2O2Solution is heated to reflux 2~3h under the conditions of 100~120 DEG C, takes out postcooling extremely
Room temperature washs, filters, is dry, obtaining the modified carbon nanotube in surface by conventional method；
2) reduction process is impregnated, carbon nano-tube material modified is crushed, is impregnated 12~24 hours with ruthenium saline solution, then
It is restored, is washed with deionized to neutrality with reducing agent, then be dried, obtain ruthenium catalyst；
3) ruthenium catalyst roasting process roasts ruthenium catalyst, the ruthenium-based catalyst aoxidized；
4) ruthenium-based catalyst by the oxidation that step 3) obtains is added in reaction kettle, is passed through hydrogen displacement reaction gas, is carried out
Activation is hydrogenated, reaction temperature is 10~40 DEG C, preferably 20~30 DEG C, maintains reaction gauge pressure for 0~1.0MPaG, preferably 0.1~
0.5MPaG, the reaction time be 6~for 24 hours, preferably 8~12h.
7. the technique of reactive distillation synthesis menthones according to claim 6, it is characterised in that：It is described in step 2)
Ruthenium salt be set as ruthenium trichloride or ruthenium hydrochloride sodium or carbonyl ruthenic chloride, the ruthenium salinity is 5~15g/L.
8. the technique of reactive distillation synthesis menthones according to claim 6, it is characterised in that：It is described in step 2)
Reducing agent be set as one kind in hydrazine hydrate, potassium borohydride, formaldehyde.
9. the technique of reactive distillation synthesis menthones according to claim 6, it is characterised in that：In the step 3)
In, calcination temperature is set as 200~600 DEG C, and roasting time is set as 3~5 hours.
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| CN109293487A (en) * | 2018-10-10 | 2019-02-01 | 万华化学集团股份有限公司 | A method of preparing menthones |
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| CN109593029A (en) * | 2018-11-26 | 2019-04-09 | 万华化学集团股份有限公司 | A kind of method preparing high-purity L- menthones and the catalyst system for this method |
| CN109593029B (en) * | 2018-11-26 | 2022-01-07 | 万华化学集团股份有限公司 | Method for preparing high-purity L-menthone and catalyst system used for method |
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