CN105562041A - Preparation method of solid alkali catalyst and reaction method for catalytic synthesis of ionone fragrance intermediate by solid alkali catalyst - Google Patents
Preparation method of solid alkali catalyst and reaction method for catalytic synthesis of ionone fragrance intermediate by solid alkali catalyst Download PDFInfo
- Publication number
- CN105562041A CN105562041A CN201510936416.9A CN201510936416A CN105562041A CN 105562041 A CN105562041 A CN 105562041A CN 201510936416 A CN201510936416 A CN 201510936416A CN 105562041 A CN105562041 A CN 105562041A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- solid base
- base catalyst
- ionone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a solid alkali catalyst and a reaction method for the catalytic synthesis of an ionone fragrance intermediate by the solid alkali catalyst. The preparation method of the solid alkali catalyst comprises the following steps: putting a carrier in a flask, adding KF (Potassium Fluoride) aqueous solution, stirring for 4-9h at the temperature of 40-80DEG C in an ultrasonic oscillator, then, stirring at the temperature of 89-99DEG C until a mixture is viscous, drying the mixture, roasting for 4-7h at the temperature of 400-600DEG C, and cooling to obtain the solid alkali catalyst which loads KF on the carrier, wherein the carrier is one of aluminium oxide or magnesium oxide or calcium oxide. Since an ultrasonic-assisted excessive dipping method is adopted to prepare the solid alkali catalyst, the loading capability and the dipping rate of active components are effectively improved. In addition, when the solid alkali catalyst prepared with the preparation method is used for carrying out the catalytic synthesis of the ionone fragrance intermediate, a subsequent alkali neutralization operation carried out when liquid alkali catalyst is used is avoided, cost is lowered, sewage is reduced, catalytic reaction has a high yield, the catalyst and a product can be easily separated, and the catalyst can be repeatedly used.
Description
Technical field
The present invention relates to a kind of preparation method of the solid base catalyst for catalyzing and synthesizing irisone system fragrance intermediates, and synthesize the reaction method of irisone system fragrance intermediates with this catalyst.
Background technology
Current pseudo ionone and methyl pseudo-ionone are the important intermediate of synthesis irisone, are widely used in spices, medicine, food additives industry.Irisone is a kind of rare spice with banksia rose type fragrance, and be one of maximum and of paramount importance spices of output in perfume industry, the alpha, beta-lonone simultaneously synthesized is the important intermediate of synthetic vitamin A and beta carotene.
Catalyst conventional in traditional synthesis technique is liquid caustic soda catalyst, as the NaOH aqueous solution and Ba(OH)
2saturated aqueous solution, also has the alcoholic solution system such as EtONa/EtOH, NaOH/EtOH, KOH/MeOH, current industrial conventional be the NaOH aqueous solution.Use the major defect of these liquid caustic soda catalyst to be catalyst recycling difficulties, equipment corrosion is large, the problems such as serious environmental pollution.In order to overcome above-mentioned deficiency, Chinese scholars is exploring the linguistic term of the synthesis technique to pseudo ionone and homologue thereof always, and current general thinking replaces liquid caustic soda catalyst with solid base catalyst, uses many as hydrotalcite and MgO and Al
2o
3immobilized KNO on carrier
3, KOH, K
2cO
3kF even load type base catalyst, not only can realize the catalytic reaction process of high activity, high selectivity, catalyst is easy to recycle, and solves a series of problem of environmental pollution, but solid base catalyst prepared by existing method floods because of just simple during making, ultrasonic wave is not utilized to carry out booster action, so the Active components distribution existed in load is uneven, and content is low, uncontrollable, causes the problems such as the poor reproducibility of catalyst preparing.
When another existing liquid caustic soda catalyst synthesis pseudo ionone and homologue thereof, the troublesome poeration of follow-up neutralization bases, cost is high, and contaminated environment.
Summary of the invention
The object of the invention is to for above-mentioned existing problems and deficiency, there is provided a kind of make use of that ultrasonic wave effectively promotes active component on carrier dexterously dispersed, improve the preparation method of solid base catalyst of the load capacity of active component and infusing rate, preparation process favorable reproducibility.And this catalyst for catalyzing and synthesizing the reaction method of irisone system fragrance intermediates time, catalyst amount is little, and catalytic reaction yield is high, the easily separated regeneration of catalyst.
Technical scheme of the present invention is achieved in that
The preparation method of solid base catalyst of the present invention, be characterized in comprising the following steps: carrier is placed in flask, add the KF aqueous solution again, in ultrasonic oscillator, 40-80 DEG C is stirred 4-9h, then be stirred to thick at 89-99 DEG C, dry, (namely heating solvent evaporated), again at 400-600 DEG C of roasting 4-7h, the solid base catalyst of the supported on carriers KF for catalyzing and synthesizing irisone system fragrance intermediates is obtained after cooling, wherein said carrier is one of them of aluminium oxide or magnesia or calcium oxide, the KF2H in the described KF aqueous solution
2the quality of O is 0.5-3 times of carrier quality.
Catalyze and synthesize the reaction method of irisone system fragrance intermediates with solid base catalyst of the present invention, be characterized in comprising the steps:
(1), in there-necked flask, acetone or butanone is added; add solid base catalyst again; return stirring; under rising to reaction temperature 40-57 DEG C (herein for adopting temperature during acetone reaction) or 60-79 DEG C of (herein for adopting temperature during butanone reaction) condition; citral is dripped from constant pressure funnel; control rate of addition is 1s/1d; drip and continue reaction 3-8h; after reaction terminates; citral conversion ratio 85-100%; pseudo ionone or methyl pseudo-ionone selective be 85-98%, wherein the mass ratio of citral and solid base catalyst is 1-5:1; The mass ratio of acetone or butanone and solid base catalyst is 7-11:1.
(2), with after the course of reaction described in reacted solid base catalyst repetition step () of step () 3-5 time, collect reacted solid base catalyst, regenerate.
Described solid base catalyst renovation process is separated by reacted catalyst filtration, and by washed with methanol 3-5 time, collect filter cake and put into Muffle furnace, 300-400 DEG C of calcination process and get final product.
The method of the present invention owing to adopting the excessive infusion process of ultrasonic assistant to prepare the solid base catalyst of supported on carriers KF, what make use of that ultrasonic wave effectively promotes active component on carrier dexterously is dispersed, improves load capacity and the infusing rate of active component.The present invention also uses the method for heating solvent evaporated to make the stable load of active component controlled, and forms new catalytic active center by simple high-temperature roasting, and reactions steps is few, and operation is simple and favorable reproducibility, is beneficial to the needs of suitability for industrialized production.And when the solid base catalyst that the excessive infusion process of the ultrasonic assistant using the present invention to improve prepares catalyzes and synthesizes false irisone and homologue thereof, avoid the operation of follow-up neutralization bases when using liquid caustic soda catalyst, reduce cost, decrease sewage, catalytic reaction yield is high, catalyst and product are easy to be separated and catalyst is reusable, and the catalyst catalytic performance after regeneration is stablized, and can realize the High-efficient Production of the high selectivity high conversion of product.The invention provides the catalyst of technical scheme for inactivation after reaction in addition, by high-temperature roasting, the carbon distribution material (organic compound containing carbonyl, methyl, methylene and hydroxyl) etc. in inactivation loaded catalyst had the by-product destruction of the catalytic reaction of certain polarity, catalyst after inactivation is regenerated, catalyst catalytic performance after regeneration is stablized, basic close to or reach the catalytic effect of identical new controlling catalyst, removal process is simple to operate, solve a series of contingency questions brought by liquid caustic soda, environmental protection.
Detailed description of the invention
The preparation method of solid base catalyst of the present invention, be characterized in comprising the following steps: carrier is placed in flask, add the KF aqueous solution again, in ultrasonic oscillator, 40-80 DEG C is stirred 4-9h, then be stirred to thick at 89-99 DEG C, dry, (namely adopting the mode of heating solvent evaporated), again at 400-600 DEG C of roasting 4-7h, the solid base catalyst of the supported on carriers KF for catalyzing and synthesizing irisone system fragrance intermediates is obtained after cooling, wherein said carrier is one of them of aluminium oxide or magnesia or calcium oxide, KF2H in the described KF aqueous solution
2the quality of O is 0.5-3 times of carrier quality.
Catalyze and synthesize the reaction method of irisone system fragrance intermediates with solid base catalyst of the present invention, be characterized in comprising the steps:
(1), in there-necked flask, acetone or butanone is added; add solid base catalyst again; return stirring, under rising to reaction temperature 40-57 DEG C or 60-79 DEG C of condition, drips citral from constant pressure funnel; control rate of addition is 1s/1d; drip and continue reaction 3-8h, after reaction terminates, citral conversion ratio 85-100%; pseudo ionone or methyl pseudo-ionone selective be 85-98%, wherein the mass ratio of citral and solid base catalyst is 1-5:1; The mass ratio of acetone or butanone and solid base catalyst is 7-11:1.
(2), with after the course of reaction described in reacted solid base catalyst repetition step () of step () 3-5 time, collect reacted solid base catalyst, regenerate.
Described solid base catalyst renovation process is separated by reacted catalyst filtration, and by washed with methanol 3-5 time, collect filter cake and put into Muffle furnace, 300-400 DEG C of calcination process and get final product.
The maximum advantage of this technique is the preparation process favorable reproducibility of catalyst; Catalytic reaction yield is high, and catalyst and product are easy to be separated and catalyst is reusable, and the catalyst catalytic performance after regeneration is stablized.
Mode below by embodiment further illustrates the present invention, but does not form any limitation of the invention, and the amendment of anyone limited number of time made in right of the present invention is still in right of the present invention.
embodiment 1
The preparation method of solid base catalyst of the present invention, comprises the following steps: the Al taking 10.00g
2o
3carrier in flask, by the KF2H of 5.81g
2o is dissolved in 40g water, and mixing adds in flask, and in ultrasonic oscillator, 60 DEG C are stirred 5h, and latter 90 DEG C are stirred to thick; Take out after sediment 80 DEG C of dry 12h, in Muffle furnace, 400 DEG C of roasting 5h, cool naturally in drier, obtain 14.21g load type solid body base catalyst KF/Al
2o
31(abbreviation catalyst).
Above-mentioned catalyst is as follows for the method catalyzing and synthesizing the reaction of false irisone:
1) 40.89g acetone is added in there-necked flask, 5.42g catalyst KF/Al
2o
31, return stirring, under rising to reaction temperature 50 DEG C of conditions, drip 10.35g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 5h.After reaction terminates, obtain citral conversion ratio 86.23%, pseudo ionone is selective is 92.79%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 30.58%, and pseudo ionone is selective is 65.24%.After decaying catalyst normal temperature constant weight, quality is 6.15g.
3) by above-mentioned decaying catalyst isolated by filtration, and by washed with methanol 3 times, collect filter cake and put into Muffle furnace, 350 DEG C of calcination process 3h, dry 2h in drying box, finally obtaining catalyst quality is 5.17g, by the method reaction described in step 1), obtain citral conversion ratio 83.14%, pseudo ionone is selective is 91.37%.
embodiment 2
Solid base catalyst of the present invention, comprises the steps: that the MgO carrier taking 10.07g is in flask, by the KF2H of 11.65g
2o is dissolved in 40g water, and mixing adds in flask, and in ultrasonic oscillator, 70 DEG C are stirred 6h, and latter 93 DEG C are stirred to thick; Take out after sediment 80 DEG C of dry 12h, in Muffle furnace, 500 DEG C of roasting 6h, cool naturally in drier, obtain 18.13g load type solid body base catalyst KF/MgO
1(abbreviation catalyst).
The method that above-mentioned catalyst is used for the reaction of catalytic synthesis of methyl pseudo ionone is as follows:
1), 43.83g butanone is added, 5.39g catalyst KF/MgO in there-necked flask
1.Return stirring, under rising to reaction temperature 70 DEG C of conditions, drip 20.49g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 6h.After reaction terminates, obtain citral conversion ratio 91.68%, methyl pseudo-ionone is selective is 89.34%.
2), used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 35.27%, and methyl pseudo-ionone is selective is 50.68%.After decaying catalyst normal temperature constant weight, quality is 6.89g.
3) by above-mentioned decaying catalyst isolated by filtration, and by washed with methanol 3 times, collect filter cake and put into Muffle furnace, 400 DEG C of calcination process 3h, dry 2h in drying box, finally obtaining catalyst quality is 5.05g, by the method reaction described in step 1), obtain citral conversion ratio 90.29%, methyl pseudo-ionone is selective is 86.58%.
embodiment 3
Solid base catalyst of the present invention, comprises the following steps: the CaO carrier taking 10.03g in flask, by the KF2H of 17.43g
2o is dissolved in 40g water, and mixing adds in flask, and in ultrasonic oscillator, 80 DEG C are stirred 3h, and latter 95 DEG C are stirred to thick; Take out after sediment 80 DEG C of dry 12h, in Muffle furnace, 600 DEG C of roasting 4h, cool naturally in drier, obtain 22.21g load type solid body base catalyst KF/CaO
1(catalyst).
Above-mentioned catalyst is as follows for the method catalyzing and synthesizing the reaction of false irisone:
1) 47.25g acetone is added in there-necked flask, 5.28g catalyst KF/CaO
1.Return stirring, under rising to reaction temperature 56 DEG C of conditions, drip 25.54g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 8h.After reaction terminates, obtain citral conversion ratio 90.15%, pseudo ionone is selective is 85.36%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 41.24%, and pseudo ionone is selective is 57.35%.After decaying catalyst normal temperature constant weight, quality is 5.89g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 300 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 5.06g, by the method reaction described in step 1), obtain citral conversion ratio 87.69%, pseudo ionone is selective is 84.75%.
embodiment 4
Solid base catalyst of the present invention, comprises the following steps:: the Al taking 10.08g
2o
3carrier in flask, by the KF2H of 23.25g
2o is dissolved in 40g water, and mixing adds in flask, and in ultrasonic oscillator, 50 DEG C are stirred 8h, and latter 97 DEG C are stirred to thick; Take out after sediment 80 DEG C of dry 12h, in Muffle furnace, 400 DEG C of roasting 7h, cool naturally in drier, obtain 26.28g load type solid body base catalyst KF/Al
2o
32(abbreviation catalyst).
The method that above-mentioned catalyst is used for the reaction of catalytic synthesis of methyl pseudo ionone is as follows:
1) 52.27g butanone is added in there-necked flask, 5.26g catalyst KF/Al
2o
32.Return stirring, under rising to reaction temperature 75 DEG C of conditions, drip 15.17g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 4h.After reaction terminates, obtain citral conversion ratio 92.47%, methyl pseudo-ionone is selective is 89.36%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 25.16%, and methyl pseudo-ionone is selective is 70.28%.After decaying catalyst normal temperature constant weight, quality is 5.85g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 350 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 5.05g, by the method reaction described in step 1), obtain citral conversion ratio 91.37%, methyl pseudo-ionone is selective is 87.56%.
embodiment 5
Solid base catalyst of the present invention, comprises the following steps:: the MgO carrier taking 10.10g in flask, by the KF2H of 29.01g
2o is dissolved in 40g water, and mixing adds in flask, and in ultrasonic oscillator, 40 DEG C are stirred 8h, and latter 99 DEG C are stirred to thick; Take out after sediment 80 DEG C of dry 12h, in Muffle furnace, 500 DEG C of roasting 4h, cool naturally in drier, obtain 30.32g load type solid body base catalyst KF/MgO
2(abbreviation catalyst).
Above-mentioned catalyst is as follows for the method catalyzing and synthesizing the reaction of false irisone:
1) 50.57g acetone is added in there-necked flask, 5.39g catalyst KF/MgO
2.Return stirring, under rising to reaction temperature 40 DEG C of conditions, drip 23.12g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 7h.After reaction terminates, obtain citral conversion ratio 93.52%, pseudo ionone is selective is 85.18%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 20.51%, and pseudo ionone is selective is 47.52%.After decaying catalyst normal temperature constant weight, quality is 6.56g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 400 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 5.13g, by the method reaction described in step 1), obtain citral conversion ratio 92.84%, pseudo ionone is selective is 84.86%.
embodiment 6
Solid base catalyst of the present invention, comprises the following steps: the CaO carrier taking 10.02g in flask, by the KF2H of 17.43g
2o is dissolved in 40g water, and mixing adds in flask, and in ultrasonic oscillator, 80 DEG C are stirred 4h, and latter 98 DEG C are stirred to thick; Take out after sediment 80 DEG C of dry 12h, in Muffle furnace, 600 DEG C of roasting 5h, cool naturally in drier, obtain 22.45g load type solid body base catalyst KF/CaO
2(abbreviation catalyst).
The method that above-mentioned catalyst is used for the reaction of catalytic synthesis of methyl pseudo ionone is as follows:
1) 56.72g butanone is added in there-necked flask, 5.73g catalyst KF/CaO
2.Return stirring, under rising to reaction temperature 60 DEG C of conditions, drip 7.35g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 6h.After reaction terminates, obtain citral conversion ratio 94.73%, methyl pseudo-ionone is selective is 87.52%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 38.63%, and methyl pseudo-ionone is selective is 49.84%.After decaying catalyst normal temperature constant weight, quality is 6.34g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 300 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 5.49g, by the method reaction described in step 1), obtain citral conversion ratio 92.86%, methyl pseudo-ionone is selective is 86.93%.
embodiment 7
Solid base catalyst of the present invention, comprises the following steps: the Al taking 10.04g
2o
3carrier in flask, by the KF2H of 9.93g
2o is dissolved in 40g water, and mixing adds in flask, and in ultrasonic oscillator, 70 DEG C are stirred 6h, and latter 96 DEG C are stirred to thick; Take out after sediment 80 DEG C of dry 12h, in Muffle furnace, 450 DEG C of roasting 6h, cool naturally in drier, obtain 17.01g load type solid body base catalyst KF/Al
2o
33(abbreviation catalyst).
Above-mentioned catalyst is as follows for the method catalyzing and synthesizing the reaction of false irisone:
1) 50.48g acetone is added in there-necked flask, 5.31g catalyst KF/Al
2o
33.Return stirring, under rising to reaction temperature 60 DEG C of conditions, drip 5.93g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 4h.After reaction terminates, obtain citral conversion ratio 100.00%, pseudo ionone is selective is 97.79%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 27.64%, and pseudo ionone is selective is 42.68%.After decaying catalyst normal temperature constant weight, quality is 6.29g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 30 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 4.97g, by the method reaction described in step 1), obtain citral conversion ratio 98.53%, pseudo ionone is selective is 96.73%.
embodiment 8
Solid base catalyst of the present invention, comprises the following steps: the MgO carrier taking 10.05g in flask, by the KF2H of 11.94g
2o is dissolved in 40g water, and mixing adds in flask, and in ultrasonic oscillator, 60 DEG C are stirred 7h, and latter 94 DEG C are stirred to thick; Take out after sediment 80 DEG C of dry 12h, in Muffle furnace, 550 DEG C of roasting 5h, cool naturally in drier, obtain 18.41g load type solid body base catalyst KF/MgO
3(abbreviation catalyst).
The method that above-mentioned catalyst is used for the reaction of catalytic synthesis of methyl pseudo ionone is as follows:
1) 59.73g butanone is added in there-necked flask, 5.62g catalyst KF/MgO
3.Return stirring, under rising to reaction temperature 79 DEG C of conditions, drip 13.38g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 3h.After reaction terminates, obtain citral conversion ratio 91.63%, methyl pseudo-ionone is selective is 94.29%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 38.72%, and methyl pseudo-ionone is selective is 48.62%.After decaying catalyst normal temperature constant weight, quality is 6.94g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 350 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 4.73g, by the method reaction described in step 1), obtain citral conversion ratio 90.39%, methyl pseudo-ionone is selective is 93.73%.
embodiment 9
Solid base catalyst of the present invention, comprises the following steps: the CaO carrier taking 10.07g in flask, by the KF2H of 17.87g
2o is dissolved in 40g water, and mixing adds in flask, and in ultrasonic oscillator, 50 DEG C are stirred 2h, and latter 92 DEG C are stirred to thick; Take out after sediment 80 DEG C of dry 12h, in Muffle furnace, 400 DEG C of roasting 6h, cool naturally in drier, obtain 22.58g load type solid body base catalyst KF/CaO
3(abbreviation catalyst).
Above-mentioned catalyst is as follows for the method catalyzing and synthesizing the reaction of false irisone:
1) 52.57g acetone is added in there-necked flask, 5.73g catalyst KF/CaO
3.Return stirring, under rising to reaction temperature 50 DEG C of conditions, drip 17.73g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 8h.After reaction terminates, obtain citral conversion ratio 90.15%, pseudo ionone is selective is 85.36%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 41.24%, and pseudo ionone is selective is 57.35%.After decaying catalyst normal temperature constant weight, quality is 6.87g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 400 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 4.92g, by the method reaction described in step 1), obtain citral conversion ratio 87.69%, pseudo ionone is selective is 84.75%.
embodiment 10
Solid base catalyst of the present invention, comprises the following steps: the Al taking 10.02g
2o
3carrier in flask, by the KF2H of 20.85g
2o is dissolved in 40g water, and mixing adds in flask, and in ultrasonic oscillator, 40 DEG C are stirred 5h, and latter 90 DEG C are stirred to thick; Take out after sediment 80 DEG C of dry 12h, in Muffle furnace, 450 DEG C of roasting 5h, cool naturally in drier, obtain 24.62g load type solid body base catalyst KF/Al
2o
34(abbreviation catalyst).
The method that above-mentioned catalyst is used for the reaction of catalytic synthesis of methyl pseudo ionone is as follows:
1) 49.24g butanone is added in there-necked flask, 5.83g catalyst KF/Al
2o
34.Return stirring, under rising to reaction temperature 75 DEG C of conditions, drip 21.17g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 6h.After reaction terminates, obtain citral conversion ratio 97.32%, methyl pseudo-ionone is selective is 86.87%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 39.28%, and methyl pseudo-ionone is selective is 52.19%.After decaying catalyst normal temperature constant weight, quality is 5.85g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 300 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 4.01g, by the method reaction described in step 1), obtain citral conversion ratio 96.93%, methyl pseudo-ionone is selective is 82.72%.
comparative example 1
Existing excessive infusion process prepares KF/Al
2o
3reaction method for catalyzing and synthesizing irisone system fragrance intermediates is as follows:
Another kind provided by the invention is for catalyzing and synthesizing the catalyst KF/Al of irisone system fragrance intermediates
2o
3, obtained by following step: the Al taking 10.02g
2o
3carrier in flask, by the KF2H of 20.85g
2o is dissolved in 40g water, mixing add in flask, 40 DEG C stir 6h, after filtration washing, by sediment 80 DEG C of dry 12h, after in Muffle furnace 450 DEG C of roasting 5h, naturally cool in drier, obtain 14.19g load type solid body base catalyst KF/Al
2o
3.
Above-mentioned catalyst KF/Al
2o
3method for the reaction of catalytic synthesis of methyl pseudo ionone is as follows:
1) 49.24g butanone is added in there-necked flask, 5.83g catalyst KF/Al
2o
3.Return stirring, under rising to reaction temperature 75 DEG C of conditions, drip 21.17g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 6h.After reaction terminates, obtain citral conversion ratio 78.84%, methyl pseudo-ionone is selective is 80.72%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 18.73%, and methyl pseudo-ionone is selective is 31.95%.After decaying catalyst normal temperature constant weight, quality is 6.05g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 300 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 5.21g, by the method reaction described in step 1), obtain citral conversion ratio 75.29%, methyl pseudo-ionone is selective is 72.78%.
comparative example 2
It is as follows for the reaction method catalyzing and synthesizing irisone system fragrance intermediates that existing excessive infusion process prepares KF/MgO:
Another kind provided by the invention, for catalyzing and synthesizing the catalyst KF/MgO of irisone system fragrance intermediates, is obtained by following step: the MgO carrier taking 10.10g in flask, by the KF2H of 29.01g
2o is dissolved in 40g water, mixing add in flask, 40 DEG C stir 9h, after filtration washing, by sediment 80 DEG C of dry 12h, after in Muffle furnace 500 DEG C of roasting 4h, naturally cool in drier, obtain 15.92g loaded catalyst KF/MgO.
Above-mentioned catalyst KF/MgO is as follows for the method catalyzing and synthesizing the reaction of false irisone:
1) 50.57g acetone is added in there-necked flask, 5.39g catalyst KF/MgO.Return stirring, under rising to reaction temperature 40 DEG C of conditions, drip 23.12g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 7h.After reaction terminates, obtain citral conversion ratio 80.18%, pseudo ionone is selective is 84.72%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 20.19%, and pseudo ionone is selective is 35.62%.After decaying catalyst normal temperature constant weight, quality is 6.28g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 400 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 5.19g, by the method reaction described in step 1), obtain citral conversion ratio 78.27%, pseudo ionone is selective is 79.82%.
comparative example 3
It is as follows for the reaction method catalyzing and synthesizing irisone system fragrance intermediates that existing excessive infusion process prepares KF/CaO:
Another kind provided by the invention, for catalyzing and synthesizing the catalyst KF/CaO of irisone system fragrance intermediates, is obtained by following step: the CaO carrier taking 10.07g in flask, by the KF2H of 17.87g
2o is dissolved in 40g water, mixing add in flask, 50 DEG C stir 3h, after filtration washing, by sediment 80 DEG C of dry 12h, after in Muffle furnace 400 DEG C of roasting 6h, naturally cool in drier, obtain 13.67g loaded catalyst KF/CaO.
Above-mentioned catalyst KF/CaO is as follows for the method catalyzing and synthesizing the reaction of false irisone:
1) 52.57g acetone is added in there-necked flask, 5.73g catalyst KF/CaO.Return stirring, under rising to reaction temperature 50 DEG C of conditions, drip 17.73g citral from constant pressure funnel, control rate of addition is 1s/1d, drips and continues reaction 8h.After reaction terminates, obtain citral conversion ratio 79.52%, pseudo ionone is selective is 80.25%.
2) used catalyst after filtration after drying without any process, continue to carry out 4 secondary responses by process conditions, final result is for obtaining citral conversion ratio 24.68%, and pseudo ionone is selective is 27.80%.After decaying catalyst normal temperature constant weight, quality is 6.43g.
3) above-mentioned decaying catalyst is put into Muffle furnace, 400 DEG C of calcination process 3h, dry 12h in drying box, finally obtaining catalyst quality is 5.56g, by the method reaction described in step 1), obtain citral conversion ratio 77.57%, pseudo ionone is selective is 78.46%.
The embodiment of the invention described above and comparative example compare known, the load capacity of the catalyst potassium fluoride adopting existing excessive infusion process to obtain is too low, and when catalyzing and synthesizing irisone system fragrance intermediates, the productive rate of product pseudo ionone or methyl pseudo-ionone is lower; And when adopting method Kaolinite Preparation of Catalyst provided by the invention, the load capacity of potassium fluoride obviously raises, and when catalyzing and synthesizing irisone system fragrance intermediates, the productive rate of product pseudo ionone or methyl pseudo-ionone has raising in various degree, and wherein embodiment 7 reaches productive rate peak.Illustrate that the excessive infusion process of ultrasonic assistant of improvement can utilize ultrasonic wave to improve load capacity and the infusing rate of active component, thus produce more strong basic activated center, the productive rate of the product that catalytic reaction is obtained increases to some extent; And the catalytic activity of catalyst is the strongest under the treatment conditions of embodiment 7; And the catalyst provided in such scheme is easy to separation and recovery and reusable, and the catalyst catalytic performance after regeneration is stablized, basic close to or reach the catalytic effect of identical fresh catalyst.
Claims (3)
1. the preparation method of a solid base catalyst, it is characterized in that comprising the following steps: carrier is placed in flask, add the KF aqueous solution, in ultrasonic oscillator, 40-80 DEG C is stirred 4-9h, then be stirred to thick at 89-99 DEG C, dry, again at 400-600 DEG C of roasting 4-7h, the solid base catalyst of the supported on carriers KF for catalyzing and synthesizing irisone system fragrance intermediates is obtained after cooling, wherein said carrier is one of them of aluminium oxide or magnesia or calcium oxide, the KF2H in the described KF aqueous solution
2the quality of O is 0.5-3 times of carrier quality.
2. catalyze and synthesize the reaction method of irisone system fragrance intermediates with solid base catalyst according to claim 1, it is characterized in that comprising the steps:
(1), in there-necked flask, acetone or butanone is added, add solid base catalyst again, return stirring, under rising to reaction temperature 40-57 DEG C or 60-79 DEG C of condition, drips citral from constant pressure funnel, control rate of addition is 1s/1d, drip and continue reaction 3-8h, after reaction terminates, citral conversion ratio is 85-100%, pseudo ionone or the selective of methyl pseudo-ionone are 85-98%, and wherein the mass ratio of citral and solid base catalyst is 1-5:1; The mass ratio of acetone or butanone and solid base catalyst is 7-11:1;
(2), with after the course of reaction described in reacted solid base catalyst repetition step () of step () 3-5 time, collect reacted solid base catalyst, then carry out catalyst regeneration.
3. solid base catalyst according to claim 2 catalyzes and synthesizes the reaction method of irisone system fragrance intermediates, it is characterized in that, described catalyst recovery process is, reacted catalyst filtration is separated, and by washed with methanol 3-5 time, collect filter cake and put into Muffle furnace, 300-400 DEG C of calcination process and get final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510936416.9A CN105562041B (en) | 2015-12-16 | 2015-12-16 | The preparation method of solid base catalyst and its reaction method for catalyzing and synthesizing irisone system fragrance intermediates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510936416.9A CN105562041B (en) | 2015-12-16 | 2015-12-16 | The preparation method of solid base catalyst and its reaction method for catalyzing and synthesizing irisone system fragrance intermediates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105562041A true CN105562041A (en) | 2016-05-11 |
| CN105562041B CN105562041B (en) | 2018-08-21 |
Family
ID=55872994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510936416.9A Active CN105562041B (en) | 2015-12-16 | 2015-12-16 | The preparation method of solid base catalyst and its reaction method for catalyzing and synthesizing irisone system fragrance intermediates |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105562041B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045831A (en) * | 2016-06-08 | 2016-10-26 | 万华化学集团股份有限公司 | Method for green synthesis of false-methyl-ionone |
| CN106905129A (en) * | 2017-03-22 | 2017-06-30 | 吴秀花 | A kind of preparation method of fragrance intermediates |
| CN107754827A (en) * | 2017-10-23 | 2018-03-06 | 广州美晨科技实业有限公司 | A kind of load type solid body base catalyst and preparation method and application |
| CN108786867A (en) * | 2017-04-28 | 2018-11-13 | 山东新和成药业有限公司 | A kind of preparation method and purposes of the hydrotalcite-like compound catalyst that fluorine anion is modified |
| CN108976108A (en) * | 2018-08-20 | 2018-12-11 | 朱晓萍 | A method of synthesis pseudo ionone |
| CN111187152A (en) * | 2020-02-28 | 2020-05-22 | 浙江工业大学 | Method for synthesizing pseudo ionone under catalysis of alkaline immobilized ionic liquid |
| CN111203229A (en) * | 2020-02-19 | 2020-05-29 | 中国科学院过程工程研究所 | Preparation method and application of supported composite oxide catalyst |
| CN113117753A (en) * | 2021-04-01 | 2021-07-16 | 万华化学集团股份有限公司 | Hydrophobic catalyst, preparation method thereof and preparation method of beta-ionone |
| CN113509946A (en) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | Supported alumina solid base catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803284A (en) * | 2005-01-10 | 2006-07-19 | 顾明兰 | Super alkali composite catalyst for preparing superfine KF/Al2O3 using Sol-gel method |
| WO2007039245A1 (en) * | 2005-09-29 | 2007-04-12 | Dsm Ip Assets B.V. | Cleavage of alkynediols |
-
2015
- 2015-12-16 CN CN201510936416.9A patent/CN105562041B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803284A (en) * | 2005-01-10 | 2006-07-19 | 顾明兰 | Super alkali composite catalyst for preparing superfine KF/Al2O3 using Sol-gel method |
| WO2007039245A1 (en) * | 2005-09-29 | 2007-04-12 | Dsm Ip Assets B.V. | Cleavage of alkynediols |
Non-Patent Citations (3)
| Title |
|---|
| 唐斯萍 等: "KF/Al2O3催化柠檬醛和丙酮缩合制备假性紫罗兰酮", 《零陵学院学报》 * |
| 杨华明著: "《无机功能材料》", 31 May 2007 * |
| 黄敏等: "负载型固体碱催化合成假性紫罗兰酮的研究", 《工业催化剂》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045831B (en) * | 2016-06-08 | 2018-06-12 | 万华化学集团股份有限公司 | A kind of green synthesis method of X-ray computed |
| CN106045831A (en) * | 2016-06-08 | 2016-10-26 | 万华化学集团股份有限公司 | Method for green synthesis of false-methyl-ionone |
| CN106905129A (en) * | 2017-03-22 | 2017-06-30 | 吴秀花 | A kind of preparation method of fragrance intermediates |
| CN108786867B (en) * | 2017-04-28 | 2021-06-15 | 山东新和成药业有限公司 | Preparation method and application of fluorine anion modified hydrotalcite-like catalyst |
| CN108786867A (en) * | 2017-04-28 | 2018-11-13 | 山东新和成药业有限公司 | A kind of preparation method and purposes of the hydrotalcite-like compound catalyst that fluorine anion is modified |
| CN107754827B (en) * | 2017-10-23 | 2020-08-07 | 广州美晨科技实业有限公司 | Supported solid base catalyst and preparation method and application thereof |
| CN107754827A (en) * | 2017-10-23 | 2018-03-06 | 广州美晨科技实业有限公司 | A kind of load type solid body base catalyst and preparation method and application |
| CN108976108A (en) * | 2018-08-20 | 2018-12-11 | 朱晓萍 | A method of synthesis pseudo ionone |
| CN111203229A (en) * | 2020-02-19 | 2020-05-29 | 中国科学院过程工程研究所 | Preparation method and application of supported composite oxide catalyst |
| CN111187152A (en) * | 2020-02-28 | 2020-05-22 | 浙江工业大学 | Method for synthesizing pseudo ionone under catalysis of alkaline immobilized ionic liquid |
| CN111187152B (en) * | 2020-02-28 | 2022-07-15 | 浙江工业大学 | Method for synthesizing pseudoionone by catalyzing alkaline immobilized ionic liquid |
| CN113509946A (en) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | Supported alumina solid base catalyst |
| CN113117753A (en) * | 2021-04-01 | 2021-07-16 | 万华化学集团股份有限公司 | Hydrophobic catalyst, preparation method thereof and preparation method of beta-ionone |
| CN113117753B (en) * | 2021-04-01 | 2022-04-19 | 万华化学集团股份有限公司 | Hydrophobic catalyst, preparation method thereof and preparation method of beta-ionone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105562041B (en) | 2018-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105562041A (en) | Preparation method of solid alkali catalyst and reaction method for catalytic synthesis of ionone fragrance intermediate by solid alkali catalyst | |
| CN108440463A (en) | A method of preparing 5 hydroxymethyl furfural with load type metal molecular sieve catalyst catalysis | |
| CN105622419B (en) | A kind of method that carbohydrate prepares ethyl glycolate | |
| CN108689837A (en) | A kind of method that one kettle way catalysis furfural prepares ethyl levulinate | |
| CN108976108A (en) | A method of synthesis pseudo ionone | |
| CN100569726C (en) | The synthesis technique of mesitylene carboxylic acid | |
| CN108043456A (en) | A kind of polyacid class ionic-liquid catalyst, preparation method and the method for preparing cyclohexanol with its catalysis ethyl cyclohexyl ester hydrolysis | |
| CN104447672A (en) | Method for synthesizing epsilon-caprolactone by using active carbon immobilized heteropoly acid | |
| CN107286006A (en) | A kind of method that catalyzed alcoholysis lignin prepares Acetovanillone and acetosyringone | |
| CN104447204B (en) | A kind of method preparing glycol | |
| JPH0325224B2 (en) | ||
| CN110252406A (en) | A kind of catalyst and preparation method thereof of oxidation of ethanol carbonylation synthesizing diethyl carbonate | |
| CN102389800A (en) | Catalyst for use in preparation of 1,2-propanediol by low-temperature low-pressure hydrogenation of biological glycerol and preparation method thereof | |
| CN105130814B (en) | A kind of method that pyrovinic acid catalysis prepares diethyl sebacate | |
| CN106632161A (en) | Method used for preparing gamma-valerolactone via high-selectivity catalysis | |
| CN108640829A (en) | A kind of method that aqueous catalysis Oxidation of Lactic prepares pyruvic acid | |
| CN108640822B (en) | Preparation method of 4-vinyl guaiacol and 4-vinyl guaiacol | |
| CN106552670B (en) | A kind of bigger serface slightly solubility heteropoly acid copper salt catalyst, preparation method and its application | |
| CN108440270A (en) | A kind of synthetic method of 2,3,3,3- tetrafluoros propionic acid | |
| CN104475110B (en) | Catalyst for preparing Guerbet alcohol and preparation method for catalyst for preparing Guerbet alcohol | |
| WO2020238470A1 (en) | Catalyst capable of effectively catalyzing conjugated linoleic acid synthesis, preparation method and method of catalyzing conjugated linoleic acid synthesis | |
| CN104693023B (en) | A kind of method that biomass sugar prepares levulinate | |
| CN107952479A (en) | A kind of functionalization more acids ionic-liquid catalyst, preparation method and the methods with its catalysis cyclohexene direct esterification | |
| CN110157545A (en) | The method that tungsten-based catalyst is catalyzed natural oil oxicracking preparation Short-Chain Fatty Acids and its derivative | |
| CN109627168A (en) | A kind of preparation method of tributyl citrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhong Lianjun Inventor after: Yao Qia Inventor after: Zhang Jianbin Inventor before: Yao Qia Inventor before: Zhang Jianbin Inventor before: Li Zehong |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |