CN102807482B - Production process and device for preparing irone by using pseudoionone - Google Patents
Production process and device for preparing irone by using pseudoionone Download PDFInfo
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- CN102807482B CN102807482B CN2012102983569A CN201210298356A CN102807482B CN 102807482 B CN102807482 B CN 102807482B CN 2012102983569 A CN2012102983569 A CN 2012102983569A CN 201210298356 A CN201210298356 A CN 201210298356A CN 102807482 B CN102807482 B CN 102807482B
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- 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
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Abstract
The invention discloses a production process and a device for preparing irone by using pseudoionone. The production process comprises the steps: reacting the pseudoionone with diiodomethane under a catalytic action of zinc copper couple, so as to obtain 9,10-cyclo-methylene pseudoionone; and carrying out low-temperature ring-closure reaction on the 9,10-cyclo-methylene pseudoionone under the catalyzing of a superacid so as to obtain the irone. A production device for preparing the irone by using the pseudoionone, disclosed by the invention, comprises an ammonium chloride storage tank, a diethyl ether storage tank, a mixing tank, a dichloromethane storage tank, a reaction tank I, a middle storage tank I, a material transporting pump I, a distiller I, a middle storage tank II, a material transporting pump II, an alkali liquor storage tank, a reaction tank II, a middle storage tank III, a material transporting pump III, a distiller II, a condensation cooler and a product storage tank. According to the process and the device, the process line is relatively short, the selectivity of methyl positioning is good, the total yield of the irone is high, alpha- irone content in the irone is high, the fragrant is good, and the irone product quality is high.
Description
Technical field
The present invention relates to a kind of production technique and device for preparing Methylionone, especially relate to production technique and device that a kind of citrylideneacetone prepares Methylionone.
Background technology
Methylionone is colourless or little yellow transparent liquid, have soft fragrant and sweet, fragrance is pure and fresh pure, is the most high-grade a kind of in the jononeionone series rare spice of generally acknowledging in the world, is used for the flavouring of the products such as makeup, skin care product, food, cigarette, perfumed soap, clothing, paper and painting and calligraphy.Methylionone mainly exists with three kinds of isomer (α-type, β-type, γ-type) form, and different isomer has different aroma characteristics, and the structural formula of three kinds of isomer is as follows:
Wherein have most the characteristic of natural Methylionone congealed fat with α-type, fragrance is simple and elegant and expensive, and therefore, α-Methylionone content is higher, and its price is higher.
The plant production cycle of extracting natural Methylionone reaches 6 ~ 7 years, yields poorly, demand that can not satisfying the market, and therefore, the Methylionone of synthetic has larger market.
at present, the synthetic multiselect citral of Methylionone is raw material, main technique is (the Barton D.H.R. such as Barton, Mousseron-Cantet M. A Synthesis of irone. J Chem Soc. 1960, 271 ~ 272) and (the Torii S. such as Torii, Uneyame K., Matsunami S. Steroselective Synthesis of (±)-Irone. J Org Chem, 1980, 45:16 ~ 20) the ethylene linkage epoxidation that proposes, Grignard reagent methyl location, strong acid or Lewis acid close the industrialized producing technology of ring, these synthesis techniques, synthetic route is long, complex operation, the Methylionone yield is low, α-Methylionone content low (approximately 30% left and right), be mainly β-irone and γ-Methylionone, cause the on the low side of Methylionone.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, provides a kind of operational path brief, and the Methylionone yield is high, and the high and citrylideneacetone easily suitability for industrialized production of α in product-Methylionone content prepares production technique and the device of Methylionone.
The technical scheme that the present invention solves its technical problem employing is:
The present invention's citrylideneacetone prepares the production technique of Methylionone, under the even katalysis of zinc-copper, with the methylene iodide reaction, obtains 9,10-ring methylene radical citrylideneacetone by citrylideneacetone; 9,10-ring methylene radical citrylideneacetone is under the catalysis of super acids, and the low temperature ring-closure reaction obtains Methylionone.
Specifically comprise the following steps:
(1) citrylideneacetone reacts with methylene iodide under the effect of catalyzer zinc-copper idol, obtains 9,10-ring methylene radical citrylideneacetone:
First catalyzer zinc-copper is occasionally joined in retort, then add successively methylene chloride and ether, start agitator, under 30 ℃ ~ 50 ℃, the mixed solution of citrylideneacetone and methylene iodide is joined in retort reaction 2h ~ 10h, after reaction is completed, add saturated aqueous ammonium chloride, termination reaction, close agitator, first emit water after the profit layering, organic phase removes by filter catalyzer, and filtrate is delivered to distiller and reclaimed solvent, get 9,10-ring methylene radical citrylideneacetone;
Operation condition: the envelope-bulk to weight ratio of citrylideneacetone and catalyzer zinc-copper idol is 1: 0.5 ~ 4 (volume (L)/weight (kg)); The volume ratio of citrylideneacetone and methylene iodide is 1: 1 ~ 4; The volume ratio of citrylideneacetone and ether is 1: 2 ~ 4; The volume ratio of citrylideneacetone and methylene dichloride is 1: 10 ~ 17; The volume ratio of citrylideneacetone and saturated aqueous ammonium chloride is 1: 2 ~ 3;
(2) 9,10-ring methylene radical citrylideneacetones are under the catalysis of super acids, and the low temperature ring-closure reaction obtains Methylionone:
First super acidic catalyst is joined in retort, start agitator, add methylene dichloride, Jiang Wen adds step (1) gained 9 Dao 30 ℃ of 90 ℃ of ~ – of –, 10-ring methylene radical citrylideneacetone liquid, carry out ring-closure reaction, reaction times is 20min ~ 60min, during reaction end, adds saturated NaHCO
3Aqueous solution termination reaction, close agitator, emit organic phase after the profit layering, organic phase send the distiller underpressure distillation first to reclaim solvent, control again vacuum tightness in 133Pa ~ 1333Pa scope, temperature is to steam Methylionone under 8-15 ℃ of condition, and after condensate cooler was cooling, the cooling liqs that obtains was the Methylionone product;
Described super acidic catalyst can be sulfuric acid-sulphur trioxide, sulfuric acid-antimony pentachloride, sulfuric acid-antimony pentafluoride, fluosulfonic acid, chlorsulfonic acid, perfluorinated sulfonic resin, trifluoromethanesulfonic acid, TiO
2/ SO
4 2-Or SO
4 2-/ ZrO
2Deng super acidic catalyst;
Operation condition: the consumption of super acidic catalyst is to contain H in catalyzer
2SO
4Amount of substance calculates, 9,10-ring methylene radical citrylideneacetone and H
2SO
4Envelope-bulk to weight ratio be 100: 1 ~ 5 (volume (L)/weight (kg)); The volume ratio of 9,10-ring methylene radical citrylideneacetone and methylene dichloride is 1: 6 ~ 12; 9,10-ring methylene radical citrylideneacetone and saturated NaHCO
3The volume ratio of the aqueous solution is 1: 3 ~ 5;
Chemical reaction is all at N
2Complete under protection.
the present invention's citrylideneacetone prepares the production equipment of Methylionone, mainly comprises ammonium chloride basin, ether basin, mixing tank, methylene dichloride basin, retort I, middle vessel I, dehvery pump I, distiller I, middle vessel II, dehvery pump II, alkali lye basin, retort II, middle vessel III, dehvery pump III, distiller II, condensate cooler, product storage tank, ammonium chloride basin 1, the ether basin, mixing tank, the outlet of methylene dichloride basin is connected with retort I top inlet respectively, methylene dichloride basin bottom separately has an arm to be connected with the top inlet of retort II, there is an outlet at the middle part of retort I, be used for draining, retort I outlet at bottom is connected with the import of middle vessel I, the outlet of middle vessel I is connected with the import of dehvery pump I, the outlet of dehvery pump I is connected with distiller I centre inlet, distiller I lower part outlet is connected with the import of middle vessel II, the outlet of middle vessel II is connected with the import of dehvery pump II, the outlet of dehvery pump II is connected with retort II upper inlet, alkali lye basin lower part outlet is connected with retort II upper inlet, retort II lower part outlet is connected with the import of middle vessel III, the outlet of middle vessel III is connected with the import of dehvery pump III, the outlet of dehvery pump III is connected with distiller II centre inlet, and the top outlet of distiller II is connected with the condensate cooler import, and the condensate cooler outlet is connected with the product storage tank import.
Described ammonium chloride basin is used for the splendid attire saturated aqueous ammonium chloride, and the ether basin is used for the splendid attire ether, and mixing tank is used for the mixed solution of splendid attire methylene iodide and citrylideneacetone, and the methylene dichloride basin is used for the splendid attire methylene dichloride, and the alkali lye basin is used for the saturated NaHCO of splendid attire
3The aqueous solution, the distiller II is provided with vacuum distillation apparatus.
Described retort I and retort II are equipped with agitator, temperature sensor, pressure transmitter, pH sensor and pressure security protector; in addition, nitrogen inlet and other supplementary material import are arranged at the top, and the filtration sieve plate is equipped with in the bottom; chuck also is housed, and chuck is used for heating or cooling.
Adopt the present invention, operational path is shorter, and the selectivity that methyl is located is good, and the total recovery of Methylionone 〉=55% reaches as high as more than 67%; In product, α-Methylionone content 〉=40wt% is more than reaching as high as 60wt%; Note is good, and the Methylionone quality product is high.
Description of drawings
Fig. 1 is the production equipment schematic diagram that citrylideneacetone prepares Methylionone.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1-7 is the production technique embodiment of preparation Methylionone.
Embodiment 1
The present embodiment comprises the following steps:
(1) 9, synthesizing of 10-ring methylene radical citrylideneacetone: first 50kg zinc-copper coupled catalyst is joined in retort I 5, open successively again methylene dichloride basin 4 and ether basin 2 bottom valves, 720L methylene dichloride and 90L ether are joined in retort I 5, start retort I 5 agitators, be heated to 35 ℃, the mixed solution of the 120L methylene iodide in mixing tank 3 and 50L citrylideneacetone is joined in retort I 5, reaction 6h, after reaction is completed, open ammonium chloride basin 1 bottom valve, the 100L saturated aqueous ammonium chloride is added in retort I 5, termination reaction, close agitator, in question response tank I 5 after the profit layering, first emit water from retort I 5 top water shoots, organic phase removes by filter catalyzer through the sieve plate of retort I 5 bottoms, filtrate is stored in middle vessel I 6, with dehvery pump I 7, filtrate is pumped into distiller I 8 and reclaim solvent, get 9, 10-ring methylene radical citrylideneacetone, be stored in middle vessel II 9,
(2) 9, the synthetic Methylionone of 10-ring methylene radical citrylideneacetone ring-closure reaction: first the 2L chlorsulfonic acid is joined in retort II 12, start retort II 12 agitators, open methylene dichloride basin 4 bottom valves, the 700L methylene dichloride is joined in retort II 12, be cooled to-60 ℃, use again dehvery pump II 10 with 9 in middle vessel II 9,10-ring methylene radical citrylideneacetone 100L sends in retort II 12, carry out ring-closure reaction, after reacting 40 min, open alkali lye basin 11 bottom valves, add saturated NaHCO from alkali lye basin 11
3Aqueous solution 400L, termination reaction, close agitator, in question response tank II 12 after the profit layering, emit organic phase from retort II 12 bottoms and send into middle vessel III 13, with dehvery pump III 14, organic phase is pumped into the first decompression and solvent recovery of distiller II 15, control vacuum tightness in 133Pa ~ 1333Pa scope, temperature is to steam Methylionone under 8-15 ℃ of condition, after condensate cooler 16 is cooling again, the cooling liqs that obtains is the Methylionone product, and product is stored in product storage tank 17.
[0016]Chemical reaction is all at N
2Complete under protection.
In the present embodiment, two step total recoverys are 60%, and in the Methylionone product, the purity of Methylionone is that 97%(wherein contains α-Methylionone 61%, β-irone 27%, γ-Methylionone 9%).
Embodiment 2-7 working method is identical with embodiment 1, and other each processing parameters and yield result are as shown in table 1.
Wherein, embodiment 2 super acidic catalyst used is sulfuric acid-sulphur trioxide, embodiment 3 super acidic catalyst used is sulfuric acid-antimony pentachloride, embodiment 4 super acidic catalyst used is sulfuric acid-antimony pentafluoride, embodiment 5 super acidic catalyst used is fluosulfonic acid, embodiment 6 super acidic catalyst used is perfluorinated sulfonic resin, and embodiment 7 super acidic catalyst used is TiO
2/ SO
4 2-
Embodiment 8
The present embodiment is the production equipment embodiment that citrylideneacetone prepares Methylionone:
With reference to Fig. 1, the citrylideneacetone of the present embodiment prepares the production equipment of Methylionone, mainly comprises ammonium chloride basin 1, ether basin 2, mixing tank 3, methylene dichloride basin 4, retort I 5, middle vessel I 6, dehvery pump I 7, distiller I 8, middle vessel II 9, dehvery pump II 10, alkali lye basin 11, retort II 12, middle vessel III 13, dehvery pump III 14, distiller II 15, condensate cooler 16, product storage tank 17.ammonium chloride basin 1, ether basin 2, mixing tank 3, the outlet of methylene dichloride basin 4 is connected with retort I 5 top inlet respectively, methylene dichloride basin 4 bottoms separately have an arm to be connected with the top inlet of retort II 12, there is an outlet at the middle part of retort I 5, be used for draining, retort I 5 outlet at bottoms are connected with 6 imports of middle vessel I, 6 outlets of middle vessel I are connected with 7 imports of dehvery pump I, 7 outlets of dehvery pump I are connected with distiller I 8 centre inlet, distiller I 8 lower part outlets are connected with 9 imports of middle vessel II, 9 outlets of middle vessel II are connected with 10 imports of dehvery pump II, 10 outlets of dehvery pump II are connected with retort II 12 upper inlet, alkali lye basin 11 lower part outlets are connected with retort II 12 upper inlet, retort II 12 lower part outlets are connected with 13 imports of middle vessel III, 13 outlets of middle vessel III are connected with 14 imports of dehvery pump III, 14 outlets of dehvery pump III are connected with distiller II 15 centre inlet, the 15 top outlets of distiller II are connected with condensate cooler 16 imports, and condensate cooler 16 outlets are connected with product storage tank 17 imports.
Described ammonium chloride basin 1 is equipped with saturated aqueous ammonium chloride, and ether basin 2 is equipped with ether, and mixing tank 3 is equipped with the mixed solution of methylene iodide and citrylideneacetone, and methylene dichloride basin 4 is equipped with methylene dichloride, and alkali lye basin 11 is equipped with saturated NaHCO
3The aqueous solution, distiller II 15 is provided with vacuum distillation apparatus.
Described retort I 5 and retort II 12 are equipped with agitator, temperature sensor, pressure transmitter, pH sensor and pressure security protector; in addition, nitrogen inlet and other supplementary material import are arranged at the top, and the filtration sieve plate is equipped with in the bottom; chuck also is housed, and chuck is used for heating or cooling.
Claims (3)
1. a citrylideneacetone prepares the production technique of Methylionone, it is characterized in that, comprises the following steps:
(1) citrylideneacetone reacts with methylene iodide under the effect of catalyzer zinc-copper idol, obtains 9,10-ring methylene radical citrylideneacetone:
First catalyzer zinc-copper is occasionally joined in retort, then add successively methylene chloride and ether, start agitator, under 30 ℃ ~ 50 ℃, the mixed solution of citrylideneacetone and methylene iodide is joined in retort reaction 2h ~ 10h, after reaction is completed, add saturated aqueous ammonium chloride, termination reaction, close agitator, first emit water after the profit layering, organic phase removes by filter catalyzer, and filtrate is delivered to distiller and reclaimed solvent, get 9,10-ring methylene radical citrylideneacetone;
Operation condition: the envelope-bulk to weight ratio of citrylideneacetone and catalyzer zinc-copper idol is 1: 0.5 ~ 4; The volume ratio of citrylideneacetone and methylene iodide is 1: 1 ~ 4; The volume ratio of citrylideneacetone and ether is 1: 2 ~ 4; The volume ratio of citrylideneacetone and methylene dichloride is 1: 10 ~ 17; The volume ratio of citrylideneacetone and saturated aqueous ammonium chloride is 1: 2 ~ 3;
(2) 9,10-ring methylene radical citrylideneacetones are under the catalysis of super acids, and the low temperature ring-closure reaction obtains Methylionone:
First super acidic catalyst is joined in retort, start agitator, add methylene dichloride, Jiang Wen adds step (1) gained 9 Dao 30 ℃ of 90 ℃ of ~ – of –, 10-ring methylene radical citrylideneacetone liquid, carry out ring-closure reaction, reaction times is 20min ~ 60min, during reaction end, adds saturated NaHCO
3Aqueous solution termination reaction, close agitator, emit organic phase after the profit layering, organic phase send the distiller underpressure distillation first to reclaim solvent, control again vacuum tightness in 133Pa ~ 1333Pa scope, temperature is to steam Methylionone under 8-15 ℃ of condition, and after condensate cooler was cooling, the cooling liqs that obtains was the Methylionone product;
Operation condition: the consumption of super acidic catalyst is to contain H in catalyzer
2SO
4Amount of substance calculates, 9,10-ring methylene radical citrylideneacetone and H
2SO
4Envelope-bulk to weight ratio be 100: 1 ~ 5; The volume ratio of 9,10-ring methylene radical citrylideneacetone and methylene dichloride is 1: 6 ~ 12; 9,10-ring methylene radical citrylideneacetone and saturated NaHCO
3The volume ratio of the aqueous solution is 1: 3 ~ 5;
Chemical reaction is all at N
2Complete under protection.
2. citrylideneacetone according to claim 1 prepares the production technique of Methylionone, it is characterized in that, described super acidic catalyst is sulfuric acid-sulphur trioxide, sulfuric acid-antimony pentachloride, sulfuric acid-antimony pentafluoride, fluosulfonic acid, chlorsulfonic acid, perfluorinated sulfonic resin, trifluoromethanesulfonic acid, TiO
2/ SO
4 2-Or SO
4 2-/ ZrO
2
3. an enforcement prepares the device of Methylionone production technique as citrylideneacetone as described in one of claim 1-2, it is characterized in that, mainly comprise ammonium chloride basin, ether basin, mixing tank, methylene dichloride basin, retort I, middle vessel I, dehvery pump I, distiller I, middle vessel II, dehvery pump II, alkali lye basin, retort II, middle vessel III, dehvery pump III, distiller II, condensate cooler, product storage tank, the ammonium chloride basin, the ether basin, mixing tank, the outlet of methylene dichloride basin is connected with retort I top inlet respectively, methylene dichloride basin bottom separately has an arm to be connected with the top inlet of retort II, there is an outlet at the middle part of retort I, be used for draining, retort I outlet at bottom is connected with the import of middle vessel I, the outlet of middle vessel I is connected with the import of dehvery pump I, the outlet of dehvery pump I is connected with distiller I centre inlet, distiller I lower part outlet is connected with the import of middle vessel II, the outlet of middle vessel II is connected with the import of dehvery pump II, the outlet of dehvery pump II is connected with retort II upper inlet, alkali lye basin lower part outlet is connected with retort II upper inlet, retort II lower part outlet is connected with the import of middle vessel III, the outlet of middle vessel III is connected with the import of dehvery pump III, the outlet of dehvery pump III is connected with distiller II centre inlet, and the top outlet of distiller II is connected with the condensate cooler import, and the condensate cooler outlet is connected with the product storage tank import,
Described retort I and retort II are equipped with agitator, temperature sensor, pressure transmitter, pH sensor and pressure security protector; in addition, nitrogen inlet and other supplementary material import are arranged at the top, and the filtration sieve plate is equipped with in the bottom; chuck also is housed, and chuck is used for heating or cooling.
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| CN2012102983569A CN102807482B (en) | 2012-08-21 | 2012-08-21 | Production process and device for preparing irone by using pseudoionone |
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| CN2012102983569A CN102807482B (en) | 2012-08-21 | 2012-08-21 | Production process and device for preparing irone by using pseudoionone |
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| WO2022225459A1 (en) * | 2021-04-20 | 2022-10-27 | Agency For Science, Technology And Research | Synthesis of enantiopure cis-α-irone from a renewable carbon source |
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| US5113021A (en) * | 1989-09-21 | 1992-05-12 | Givaudan Corporation | Process for the manufacture of a mixture of α- and β-irone |
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Non-Patent Citations (4)
| Title |
|---|
| 刘晓庚 等.鸢尾酮的合成研究.《香料香精化妆品》.2001,(第2期),第5-7页. |
| 刘晓庚 等.鸢尾酮的合成路线研究.《江西农业大学学报》.1999,第21卷(第1期),第124-127页. |
| 鸢尾酮的合成研究;刘晓庚 等;《香料香精化妆品》;20010430(第2期);第5-7页 * |
| 鸢尾酮的合成路线研究;刘晓庚 等;《江西农业大学学报》;19990331;第21卷(第1期);第124-127页 * |
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