CN101381294A - Industrial production method of 1,3-cyclohexanedione - Google Patents
Industrial production method of 1,3-cyclohexanedione Download PDFInfo
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- CN101381294A CN101381294A CNA2008101719897A CN200810171989A CN101381294A CN 101381294 A CN101381294 A CN 101381294A CN A2008101719897 A CNA2008101719897 A CN A2008101719897A CN 200810171989 A CN200810171989 A CN 200810171989A CN 101381294 A CN101381294 A CN 101381294A
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- hydroresorcinol
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- cyclohexanedione
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Abstract
The invention discloses a method for industrially producing 1, 3-cyclohexanedione. The method for industrially producing the 1, 3-cyclohexanedione comprises the following steps: putting quantitative m-phenol diamine, sodium hydroxide and water into a stainless steel batch box according to the mass ratio of 1 to 0.2-0.8 to 2-3.5, introducing materials into a stainless steel reaction kettle after dissolving and when the temperature is stabilized at about 40 DEG C, and adding a modified skeletal nickel catalyst which accounts for 3 to 4 percent of the mass of the m-phenol diamine into the stainless steel reaction kettle; introducing hydrogen after vacuum pumping to keep the pressure between 3.5 and 6.5 MPa, and discharging materials after keeping the temperature between 40 and 50 DEG C for 6 to 12 hours; putting the reaction materials into a crystallizing kettle after cooling, deposition and filtration, and adding industrial hydrochloric acid with the volume of 20 to 50 percent during stirring; and discharging material liquid when the temperature is reduced to between 5 DEG C below zero and 5 DEG C; and centrifuging, and drying the material liquid to obtain the finished product of the 1,3-cyclohexanedione. The product obtained in the embodiment of the invention is pure white, the purity is 99.9 percent, the raw material conversion rate is more than 99.9 percent, and the product yield is about 95 percent.
Description
Technical field
The present invention relates to a kind of production method of medicinal compound, specifically, the present invention is a kind of industrialized preparing process of hydroresorcinol.
Background technology
At present, have been found that hydroresorcinol has purposes widely.Hydroresorcinol can be used for preparing medicines such as arrhythmia medicine, antithrombotic reagent, antitumor drug, anodyne, virucide, 5-HT antagonist.Hydroresorcinol can also be used to preparing agricultural chemicals such as low toxicity highy potent herbicide.
For the synthetic hydroresorcinol of catalytic material hydrogenation, is a kind of in the world common processes with the Resorcinol.Domesticly then declared " a kind of preparation method of hydroresorcinol " patent of invention (application number: 200510048956.X, open day on October 12nd, 2005) in 2005 and be the present domestic highest level of representative with Zhejiang Polytechnical University.Its main technical schemes is as follows: the amount of substance ratio be 1: 1～1.5 Resorcinol and inorganic strong alkali earlier in and salify, gained salt is again under the modified skeletal nickel catalyst catalysis of molybdenum mass content 0.5～5%, under 0.5～3MPa, 50～150 ℃, carry out hydrogenating reduction, the hydrogenating reduction product at room temperature carries out acidifying and rearrangement reaction with protonic acid again and obtains described 1, hydroresorcinol, described modified skeletal nickel catalyst consumption is 0.5～3% of a Resorcinol quality.
The subject matter that the method for existing synthetic hydroresorcinol exists is:
(1) purity can not satisfy derived product below 99.5%, and particularly high-end pharmaceutical prod is to the service requirements of purity;
(2) existing technology gained for class is white or faint yellow, the not obvious sticking product of crystallization, can become deep yellow very soon in storing and transit link, derived product can't be used;
(3) mineral alkali large usage quantity in the existing technology can influence operations such as aftertreatment acidifying, and supplies consumption is strengthened, and by product increases, and wastewater treatment link expense increases;
(4) the shortening process reaction temperature of existing technology is too high, needs public heat energy facilities such as supporting corresponding boiler, thereby consumes energy higher and cause to a certain degree pollution.
Summary of the invention
Advantages such as the industrialized preparing process that the purpose of this invention is to provide a kind of hydroresorcinol, this method have reaction conditions gentleness, purity height, outward appearance is good and not easy to change.
In order to realize above-mentioned goal of the invention, the present invention by the following technical solutions:
A kind of 1, the industrialized preparing process of hydroresorcinol, with amount than the quantitative Resorcinol, sodium hydroxide and the water that are 1:0.2～0.8:2～3.5, drop into the stainless steel batcher, at temperature-stable after the dissolving during 40 ℃ of left and right sides, in the importing stainless steel cauldron, add the modified skeletal nickel catalyst that accounts for Resorcinol quality 3～4%.Inhale the vacuum back end hydrogenation and keep-up pressure at 3.5～6.5MPa discharging after being incubated 6～12 hours under 40～50 ℃ of conditions.Enter crystallization kettle through cooling, precipitation, filtration, under agitation condition, add the technical hydrochloric acid of 20～50% volumes.When being cooled to-5～5 ℃, discharge feed liquid, centrifugal, oven dry promptly gets hydroresorcinol.The product of this method gained is the high purity pure white rib shape crystal of loose shape, the re-crystallization step when having omitted aftertreatment fully.
The principle of the present invention's reaction can be represented with following chemical formula:
Reaction pressure is 3.5～6.5MPa.It is insufficient that reaction pressure is crossed low hydrogenation, and the reaction times is long; Hypertonia requires too high nonsensical to equipment, safety in production.So pressure is best in above-mentioned scope.
The applicant thinks, method of the present invention can obtain above-mentioned advantage be because:
(1) temperature of reaction is at 40～50 ℃.Hydrogenation reaction is thermopositive reaction.In general, low temperature is unsuitable for hydrogenation reaction, when this point can be from relative low temperature in the reactor hydrogen gas consumption judge.This technology can be reacted in the time of 40～50 ℃ well, and reactant is quite high through quality index after the simple aftertreatment, be owing to contain metal molybdenum (its content is far below 0.5～5% of existing patent statement), and contain other several highly selective aided metal composition at this modified skeletal nickel catalyst.
(2) mass ratio of Resorcinol and inorganic strong alkali and water.The mass ratio of technical scheme of the present invention and existing patent relatively greatly reduce the consumption of inorganic strong alkali.This proportioning makes whole technology, and aftertreatment hydrochloric acid consumption significantly reduces when comprising acidifying, and significantly reduces (by product also is to cause that product is clamminess and the major cause of variable color) attached to the by-products content in the crystalline structure when making crystallization.
The invention has the advantages that:
One, product quality is improved at all:
1, outward appearance:
Color and luster: before this, the product of domestic and international nearly all manufacturer production (comprising expensive import standard specimen) all is that class is white or faint yellow, to such an extent as to a lot of client thinks that this product just should be this color and luster.And product store and transportation in color and luster also can constantly deepen, directly have influence on the use of derived product.And product of the present invention is pure white, and long storage (even tanning by the sun in the sun under for some time) only becomes off-white color, can not influence use;
Crystal: producer's product is not almost seen crystal from visual inspection at present both at home and abroad, and more sticking, is similar to paste; Visible comparatively loose, the sparkling and crystal-clear bright rib shape crystallization of product naked eyes of the present invention.The user once took white sugar and starch to liken therebetween difference.
2, purity:
Currently available products purity promptly is qualified product 97%～98% generally both at home and abroad.Can be referred to as " senior pharmaceutical grade " product as main content 〉=99%.And product main content of the present invention can reach 99.9% level, this point is from also finding out with the fusing point contrast of other products: product fusing point of the present invention is a little more than domestic and international other producer's products (about 1 ℃), and molten journey extremely short (only 1～1.5 ℃ just molten entirely), this has also verified its high purity from another point of view.
Two, react at a lower temperature:
1, makes reaction gentleness, safety more;
2, the energy, facility investment and running cost have been saved in a large number.Reduce on year-on-year basis more than 80% than the construction investment of the equal size of capacity and (to comprise other technological innovations), make that production plant is succinct more, safety, effects of energy saving and emission reduction is obvious;
Three, feed stock conversion and aftertreatment obviously improve specific efficiency:
1, feed stock conversion and product yield improve.Because it is proper that catalyzer is selected, raw material Resorcinol transformation efficiency is high in this reaction, reach more than 99.9%, and product yield now reaches about 95%, and economic benefit is very considerable;
2, owing in reaction, significantly reduced the consumption of inorganic strong alkali, this is appreciable in the industrialized production comparison process, also hydrochloric acid injected volume and production of by-products amount, wastewater treatment pressure have an immense impact on when significantly reducing the aftertreatment acidifying, and its advantage is self-evident.
Embodiment
Embodiment 1
Stainless steel at 3000L seals in the case that feeds intake, and drops into the 800kg liquid caustic soda, and 1300kg water drops into the 600kg Resorcinol under agitation condition.Treat that material fully dissolves, temperature-stable imports in the 3000L stainless steel autoclave when 40～45 ℃ of scopes.Then add the 20kg modified skeletal nickel catalyst, to close high pressure valve behind the water thorough washing from the catalyzer dedicated port.Open vacuum pump, after the vacuum that in still, reaches capacity, close vacuum valve, slowly feed plant hydrogen to 4MPa, and hydrogen make-up at any time, keep-up pressure.Observing temperature should be between 45～50 ℃.Keep-uping pressure and temperature is opened the discharging valve after 8 hours, material is being entered the precipitation storage tank, and discharge residual gas by safe evacuated tube, unloading pressure is zero, the production of preparation next batch.
Material is derived supernatant liquid and is filtered through cooling, precipitation in the precipitation storage tank, and the lower sediment catalyzer reclaims behind suction strainer.All filtrates import in the 5000L lass lining crystallization kettle, add the technical hydrochloric acid of 20～50% volumes under cooling, agitation condition.When waiting to be cooled to-5～5 ℃, emit mother liquor and crystallization and enter whizzer drip washing drying.Centrifugal end back discharging in 10 minutes, the 12 cubes of Vacuumdriers of packing into, discharging is the pure white finished product after dry 5 hours, analyzes, packs promptly.
The product of present embodiment gained is a pure white, and purity is 99.9%, feed stock conversion 99.9%, product yield 95%.
More than to provided by the present invention 1, the industrialized preparing process of hydroresorcinol is described in detail, used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that all can change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (4)
1. one kind 1, the industrialized preparing process of hydroresorcinol, it is characterized in that: with amount than the quantitative Resorcinol, sodium hydroxide and the water that are 1:0.2～0.8:2～3.5, drop into the stainless steel batcher, at temperature-stable after the dissolving during 40 ℃ of left and right sides, in the importing stainless steel cauldron, add the catalyzer that accounts for Resorcinol quality 3～4%; Vacuum, hydrogenation keep-up pressure at 3.5～6.5MPa, discharging after being incubated 6～12 hours under 40～50 ℃ of conditions of temperature of reaction; Enter crystallization kettle through cooling, precipitation, filtration, agitation condition adds the technical hydrochloric acid of 10～50% volumes down; When being cooled to-5～5 ℃, discharge feed liquid, centrifugal, oven dry promptly gets hydroresorcinol.
2. the industrialized preparing process of hydroresorcinol according to claim 1, it is characterized in that: described catalyzer is a modified raney ni.
3. the industrialized preparing process of hydroresorcinol according to claim 1, it is characterized in that: described temperature of reaction is 45～50 ℃.
4. the industrialized preparing process of hydroresorcinol according to claim 1, it is characterized in that: described pressure remains on 3.5～6.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101719897A CN101381294A (en) | 2008-10-28 | 2008-10-28 | Industrial production method of 1,3-cyclohexanedione |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101719897A CN101381294A (en) | 2008-10-28 | 2008-10-28 | Industrial production method of 1,3-cyclohexanedione |
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| CN101381294A true CN101381294A (en) | 2009-03-11 |
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| CNA2008101719897A Pending CN101381294A (en) | 2008-10-28 | 2008-10-28 | Industrial production method of 1,3-cyclohexanedione |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516050A (en) * | 2011-12-14 | 2012-06-27 | 青岛亿明翔精细化工科技有限公司 | High-quality industrial production method of 1,3-cyclohexanedione |
| CN104672069A (en) * | 2015-01-21 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Method for preparing cyclohexanone or substituted cyclohexanone |
| CN105111058A (en) * | 2015-09-25 | 2015-12-02 | 苏州龙腾万里化工科技有限公司 | Method for preparing 1, 3-cyclohexanedione |
| CN106083545A (en) * | 2016-06-06 | 2016-11-09 | 山东福尔有限公司 | A kind of preparation method of 1,3 cyclohexanediones |
| CN110818540A (en) * | 2019-11-22 | 2020-02-21 | 湖北广富林生物制剂有限公司 | Production process of 1, 3-cyclohexanedione |
| CN112574020A (en) * | 2020-12-29 | 2021-03-30 | 浙江清和新材料科技有限公司 | Preparation method of high-quality 1, 3-cyclohexanedione product |
| CN114073975A (en) * | 2020-08-21 | 2022-02-22 | 中化河北有限公司 | Nickel oxide catalyst and process for producing 1, 3-cyclohexanedione |
| CN114315539A (en) * | 2020-09-30 | 2022-04-12 | 北京颖泰嘉和生物科技股份有限公司 | Process for preparing 1, 3-cyclohexanedione |
| CN114805067A (en) * | 2022-05-19 | 2022-07-29 | 浙江科技学院 | Preparation method of prohexadione calcium intermediate |
-
2008
- 2008-10-28 CN CNA2008101719897A patent/CN101381294A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516050A (en) * | 2011-12-14 | 2012-06-27 | 青岛亿明翔精细化工科技有限公司 | High-quality industrial production method of 1,3-cyclohexanedione |
| CN102516050B (en) * | 2011-12-14 | 2014-11-26 | 青岛亿明翔精细化工科技有限公司 | High-quality industrial production method of 1,3-cyclohexanedione |
| CN104672069A (en) * | 2015-01-21 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Method for preparing cyclohexanone or substituted cyclohexanone |
| CN104672069B (en) * | 2015-01-21 | 2016-08-24 | 中国科学院兰州化学物理研究所 | A kind of Ketohexamethylene or the preparation method of substituted cyclohexanone |
| CN105111058A (en) * | 2015-09-25 | 2015-12-02 | 苏州龙腾万里化工科技有限公司 | Method for preparing 1, 3-cyclohexanedione |
| CN106083545A (en) * | 2016-06-06 | 2016-11-09 | 山东福尔有限公司 | A kind of preparation method of 1,3 cyclohexanediones |
| CN110818540A (en) * | 2019-11-22 | 2020-02-21 | 湖北广富林生物制剂有限公司 | Production process of 1, 3-cyclohexanedione |
| CN114073975A (en) * | 2020-08-21 | 2022-02-22 | 中化河北有限公司 | Nickel oxide catalyst and process for producing 1, 3-cyclohexanedione |
| CN114315539A (en) * | 2020-09-30 | 2022-04-12 | 北京颖泰嘉和生物科技股份有限公司 | Process for preparing 1, 3-cyclohexanedione |
| CN112574020A (en) * | 2020-12-29 | 2021-03-30 | 浙江清和新材料科技有限公司 | Preparation method of high-quality 1, 3-cyclohexanedione product |
| CN112574020B (en) * | 2020-12-29 | 2023-01-24 | 浙江清和新材料科技有限公司 | Preparation method of high-quality 1, 3-cyclohexanedione product |
| CN114805067A (en) * | 2022-05-19 | 2022-07-29 | 浙江科技学院 | Preparation method of prohexadione calcium intermediate |
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Application publication date: 20090311 |