CN102363608B - Method for preparing carbazole - Google Patents
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Abstract
The invention relates to a method for preparing carbazole, in particular to a method for extracting high-purity carbazole from a coarse anthracene raw material. In the invention, phenanthrene is removed by using dimethylbenzene in two steps, the dimethylbenzene removal rate is over 90 percent, the influences of dimethylbenzene on a carbazole washing process are reduced obviously, the used new chlorobenzene solvent obviously reduces the washing times of carbazole to 3 to 4 times from 7 to 8 times, the high-purity carbazole ( the content is more than 97 percent) can be prepared, and the carbazole yield of the carbazole washing process is more than 54 percent. Starting from the coarse anthracene raw material, mother solution is circulated, the once through yield of carbazole is about 40 percent, and thus, the loss of carbazole resource is reduced.
Description
Technical field
The present invention relates to a kind of method for preparing carbazole, relate to particularly the novel method of from the crude anthracene raw material, extracting the high purity carbazole.
Background technology
Carbazole is a kind of nitrogen-containing heterocycle compound, is one of composition that economic worth is the highest in the coal tar, and 90% carbazole extracts from coal tar in the world.Carbazole can be used for producing dyestuff, pigment, photo-conductor, sensitive materials, special ink etc., is widely used in the painted of automobile finish and high-temperature resistance plastice with the pigment permanent violet of carbazole production, has advantages of high temperature resistant, ultraviolet resistance.Carbazole also can be used as the raw material of stablizer, tensio-active agent, fluorescence softening agent of synthetic resins, precious metal ore flotation agent, water reducer, lubricating oil and thermal oil etc.Carbazole group has special rigid structure, has larger conjugated system and the stronger interior electron transfer capacity of molecule, therefore has remarkable thermal property and photoelectric properties.In addition, carbazole is as biologically active substance, also is the focus of research such as the application of the medicine of the diseases such as stablizer, plant hormone, antiphlogistic drug, treatment heart trouble and tumour of sterilant.Along with the fast development of chemical engineering of materials, medicine, dye industry, the demand of carbazole is year by year the trend that rises, to the purity requirement of carbazole also more and more higher (greater than 98%).At present, the output of domestic and international smart carbazole can not satisfy the growing market requirement far away.Therefore, how to improve the purity of carbazole product, increase as much as possible yield simultaneously, reduce environmental pressure and become the common target of pursuing of coal tar processing enterprise.
The main method of at present, separating anthracene and carbazole abroad has (1) rectification method: utilize the boiling point difference of anthracene, phenanthrene and carbazole to separate.But anthracene, phenanthrene, carbazole all are high boiling point, high melting compound, and the loss of be heated rear easy coking, especially anthracene is large.The employing rectification method is produced, owing to separated material need be heated to boiling temperature, therefore energy consumption is very high, and the stage number that conventional distillation needs is very high, and equipment cost is large, needs to add nonvariant boiling reagent and adopts sequence of constant boiling and rectification anthracene, phenanthrene and carbazole could be separated.(2) the molten method of potassium: the potassium fusant that utilizes carbazole is insoluble to oils and forms the characteristics of precipitation, to add Pian Zhuan caustic potash flakes behind the crude anthracene heating and melting, the hydrolysis of carbazole potassium fusant obtains thick carbazole, obtains smart carbazole after separating, wash with alkali lye, and the dimethylbenzene recrystallization obtains high-purity carbazole.But this method will consume a large amount of alkali, and produces a large amount of waste water and waste liquid, and is very high to the requirement of equipment, and the industrial production cost is high, and environmental pressure is also very large.
The solvent wash method is mainly still adopted in the production of domestic carbazole, and the method utilizes anthracene, phenanthrene, carbazole to have different solubleness and separate in certain solvent, can extract anthracene and carbazole from crude anthracene.The shortcoming and defect of aforesaid method is: at first the crude anthracene dissolving will be washed 3-4 time except luxuriant and rich with fragrance process; separating anthracene and carbazole process also will wash 2-3 time; when using benzene kind solvent to prepare pure carbazole by thick carbazole; usually also need to wash more than 7-8 time; the process solvent wash tens times more than for preparing so pure carbazole from crude anthracene; the product purity that obtains is about 93% only also, wants to prepare the smart carbazole more than 97%, also need cooperate to steam Shengji's art.Because repeatedly washing, carbazole runs off serious, and yield is low, and solvent consumption is large, and energy consumption is high.The major cause that above-mentioned situation analyze to occur is that the detersive efficiency of solvent for use in the carbazole washing process is low on the one hand, be on the other hand the removal efficient of whole technological process China and Philippines not high due to.Therefore, need to find and a kind ofly suitable wash the click solvent and the reasonably optimizing technological process could be improved present production status, when realizing high-quality products production, reduce the loss of this precious resources of carbazole.
Summary of the invention
It is dissolving crystallized that the present invention adopts new solvent systems and processing condition that crude anthracene is carried out, and prepares highly purified carbazole.
One aspect of the present invention provides a kind of method for preparing the high purity carbazole, comprises thick carbazole dissolving crystallized step in chlorobenzene.
Wherein the solid-to-liquid ratio of thick carbazole and chlorobenzene is 1: 2～1: 5; Solvent temperature is 100 ℃; Tc is 30 ℃-60 ℃.
The method for preparing the high purity carbazole provided by the invention specifically comprises the steps:
(1) take dimethylbenzene as the first solvent the crude anthracene raw material is carried out dissolving crystallized 2 times;
(2) take DMF as the second solvent carries out dissolving crystallized 1-2 time crystallized product obtained in the previous step, anthracene is separated with carbazole, obtain anthracene and thick carbazole;
(3) take chlorobenzene as the 3rd solvent the thick carbazole that made in the upper step is carried out dissolving crystallized 3-4 time, obtain the high purity carbazole.
Thick carbazole refers to remove phenanthrene through dimethylbenzene, the carbazole enriched substance that obtains after use DMF carries out anthracene and carbazole separates.
The crude anthracene raw material is the raw material that contains anthracene, phenanthrene, carbazole, obtains behind the general I carbolineum crystallisation by cooling by coal tar, and be the work in-process of coal tar processing, main component (massfraction) is anthracene 30%～40%, phenanthrene 20%～30% and carbazole 15%～20%.In China, especially in the Shanxi Province, tar resource is very abundant, and the crude anthracene raw material supply is sufficient.
Wherein, the solid-to-liquid ratio of crude anthracene raw material and dimethylbenzene is 1 in the step (1): 0.75-1: 2, and preferred 1: 1; Solvent temperature is 120 ℃; Filtration temperature is 40-80 ℃, preferred 40 ℃.
Solid-to-liquid ratio in the step (2) is 1: 1.2-1: 2; Solvent temperature is 100 ℃; Filtration temperature is 30 ℃.
Thick carbazole in the step (3) and the solid-to-liquid ratio of chlorobenzene are 1: 2～1: 5; Solvent temperature is 100 ℃; Tc is 30 ℃-60 ℃.
In a specific embodiment of the present invention, the solid-to-liquid ratio of crude anthracene raw material and dimethylbenzene in the step (1) is 1: 1 for the first time, is 1: 1.5 for the second time, and solvent temperature is 120 ℃, and filtration temperature is 40 ℃.
In a specific embodiment of the present invention, the solid-to-liquid ratio in the step (2) is 1: 1.5, and solvent temperature is 100 ℃; Tc is 30 ℃.
In a specific embodiment of the present invention, the solid-to-liquid ratio of thick carbazole (filter residue) and chlorobenzene is 1 in the step (3): 2-1: 3, and solvent temperature is 100 ℃, filtration temperature is 30 ℃.
In a specific embodiment of the present invention, the method for preparing the high purity carbazole comprises: the crude anthracene raw material is dissolved in dimethylbenzene, and 120 ℃ of lower insulation 30min are cooled to 40 ℃ of filtrations, and filter cake repeats above-mentioned crystallisation process once; The gained filter cake dissolves in the DMF solvent, and 100 ℃ of lower insulation 30min are down to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and 100 ℃ of lower insulation 30min are down to 30 ℃ of-60 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, obtain the high purity carbazole.
In the specific embodiment of the present invention, the method for preparing the high purity carbazole comprises: the crude anthracene raw material is dissolved in dimethylbenzene, and solid-to-liquid ratio is 1: 1,120 ℃ of lower insulation 30min, be cooled to 40 ℃ of filtrations, filter cake repeats above-mentioned crystallisation process once, and solid-to-liquid ratio is 1: 1.5; The gained filter cake dissolves in the DMF solvent, and solid-to-liquid ratio is 1: 1.5, and 100 ℃ of lower insulation 30min are down to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and solid-to-liquid ratio is 1: 2, and 100 ℃ of lower insulation 30min are down to 60 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, solid-to-liquid ratio was respectively 1: 5,1: 3,1: 4, and filtration temperature is respectively 60 ℃, 30 ℃, 30 ℃ and obtains the high purity carbazole.
In the specific embodiment of the present invention, the method for preparing the high purity carbazole comprises: the crude anthracene raw material is dissolved in dimethylbenzene, and 120 ℃ of lower insulation 30min are cooled to 60 ℃ of filtrations, and filter cake repeats above-mentioned crystallisation process once; The gained filter cake dissolves in the DMF solvent, and 100 ℃ of lower insulation 30min are down to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and 100 ℃ of lower insulation 30min are down to 30 ℃ of-60 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, obtain the high purity carbazole.
In the specific embodiment of the present invention, the method for preparing the high purity carbazole comprises: the crude anthracene raw material is dissolved in dimethylbenzene, and solid-to-liquid ratio is 1: 0.75,120 ℃ of lower insulation 30min, be cooled to 60 ℃ of filtrations, filter cake repeats above-mentioned crystallisation process once, and solid-to-liquid ratio is 1: 2; The gained filter cake dissolves in the DMF solvent, and solid-to-liquid ratio is 1: 2, and 100 ℃ of lower insulation 30min are down to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and solid-to-liquid ratio is 1: 2, and 100 ℃ of lower insulation 30min are down to 40 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, solid-to-liquid ratio was respectively 1: 5,1: 3,1: 3.3, and Tc is respectively 60 ℃, 30 ℃, 30 ℃, obtains the high purity carbazole.
In the specific embodiment of the present invention, the method for preparing the high purity carbazole comprises: the crude anthracene raw material is dissolved in dimethylbenzene, and 120 ℃ of lower insulation 30min are cooled to 80 ℃ of filtrations, and filter cake repeats above-mentioned crystallisation process once; The gained filter cake dissolves in the DMF solvent, and 100 ℃ of lower insulation 30min are down to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and 100 ℃ of lower insulation 30min are down to 30 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, obtain the high purity carbazole.
In the specific embodiment of the present invention, the method for preparing the high purity carbazole comprises: crude anthracene is dissolved in dimethylbenzene, and solid-to-liquid ratio is 1: 1.2,120 ℃ of lower insulation 30min, be cooled to 80 ℃ of filtrations, filter cake repeats above-mentioned crystallisation process once, and solid-to-liquid ratio is 1: 1.6; The gained filter cake dissolves in the DMF solvent, and solid-to-liquid ratio is 1: 1.2, and 100 ℃ of lower insulation 30min are down to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and solid-to-liquid ratio is 1: 3, and 100 ℃ of lower insulation 30min are down to 30 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, solid-to-liquid ratio is respectively and obtained the high purity carbazole in 1: 2,1: 2.3,1: 3.
Term among the present invention " solid-to-liquid ratio " refers to, the ratio of solid and liquid, and wherein solid adopts mass unit gram meter, and liquid adopts volume unit milliliter meter.
Adopt two steps of dimethylbenzene to remove phenanthrene among the present invention, make luxuriant and rich with fragrance decreasing ratio more than 90%, greatly reduced luxuriant and rich with fragrance impact on the carbazole washing process, the novel solvent chlorobenzene that uses simultaneously greatly reduces the washing times of carbazole, reduces to 3-4 time from 7-8 time and just can prepare high purity carbazole (content＞97%), washes the yield of click process carbazole greater than 54%, from crude anthracene, mother liquor does not circulate, and the once through yield of carbazole has reduced the loss of carbazole resource about 40%.Because the use of novel process and novel solvent, washing flow shortens, and the solvent usage quantity greatly reduces, and the recyclable recycling of solvent and do not affect washing effect, result's favorable reproducibility.The novel solvent chlorobenzene that uses among the present invention is moderate, toxicity is little, and environmental friendliness is a kind of good carbazole refining solvent.And whole washing carbazole process is insensitive to process operation parameter, in wider solid-to-liquid ratio (1: 1-5) and under the filtration temperature (30-60 ℃), can both guarantee washing effect, easy handling.
Embodiment
Specific embodiments of the invention are for better explanation content of the present invention, and do not mean that content of the present invention is limited.The crude anthracene raw material that uses in the specific embodiment is measured the content of carbazole for adopting vapor-phase chromatography from Wuhan Iron and Steel Plant (containing anthracene 42.47%, phenanthrene 19.21%, carbazole 15.97% Internal standard curve method result).
Adopting the method for gas chromatography determination carbazole content is Internal standard curve method and areas of peak normalization method dual mode, and actual conditions is as follows:
Shellomadzu (Japanese Shimadzu) GC 2014,
-5 (USA) capillary column (0.32mm x 30m), stationary phase is 5% phenylbenzene/95% dimethyl polysiloxane, stationary liquid thickness is 0.25 μ m.Use flame ionization ditector (FID), temperature: 300 ℃; Sample size 0.4 μ L.Hydrogen flowing quantity: 50kPa, air flow quantity: 50kPa, carrier gas: N
2, 75kPa.Heating schedule is: 170 ℃ keep 1min, then are raised to 200 ℃ with 3.5 ℃/min, keep 1min again, are raised to 250 ℃ with 10 ℃/min at last.Greater than 99%, carbazole standard specimen content is greater than 99.3% take 9-Fluorenone as internal standard substance content, and acetonitrile (HPLC) is the dissolution with solvents sample, adopts Internal standard curve method to carry out chromatogram quantification.Get 5 experimental points when measuring graticule, carbazole mark liquid concentration is diluted to respectively 1.4mg/mL, 1.0mg/mL, 0.6mg/mL, 0.2mg/mL, 0.05mg/mL; 9-Fluorenone is diluted to 0.6mg/mL, and remains unchanged.Respectively these five carbazole standard models are measured under above-mentioned GC condition, take sample concentration as X-coordinate, the average Ai/As of the ratio of the peak area Ai of carbazole and the peak area As of 9-Fluorenone is ordinate zou, draw mark typical curve in the carbazole, obtain marking the typical curve equation in the carbazole through linear match as follows: y=1.5896x R
2=0.9990
Carbazole percentage composition calculation formula: ω in the sample=(y*99.3%)/(1.5896*c) (1)
Wherein: ω is the percentage composition of carbazole in the sample, and y is the average of Ai/As, and c is the concentration of sample, and unit is mg/mL.
Testing sample is mixed with 0.6mg/mL during specimen, and wherein 9-Fluorenone concentration is the same with concentration in the mark product still is 0.6mg/mL, measures under same chromatographic condition, draws Ai/As, and substitution formula (1) calculates and gets final product.
Owing to all can contain a certain amount of solvent in the sample that each step obtains, for fear of Solvent effect, so adopt Internal standard curve method (calculating at same benchmark) when yield calculates.And it is same because Solvent effect, the final purity of carbazole that adopts Internal standard curve method to obtain is more much lower than actual purity, and at this moment sample purity is very high, adopts the normalized error of peak area very little, so final purity adopts the normalized result of peak area.
Example 1:
In the there-necked flask that agitator, reflux condensing tube and thermometer are housed, add 300g crude anthracene raw material, 300mL dimethylbenzene, under the agitation condition, be heated to 120 ℃ and make it dissolving, insulation 30min, be cooled to 40 ℃ of filtrations, obtain filter cake (filter cake 1) 193.46g, filter residue (filter residue 1) 112.14g; Repeat above-mentioned steps, get gained filter cake (filter cake 1) 190g, to wherein adding 285mL dimethylbenzene, under the agitation condition, 120 ℃ make it dissolving, insulation 30min, and 40 ℃ of filtrations obtain filter cake (filter cake 2) 157.82g, filter residue (filter residue 2) 34.81g; Get gained filter cake (filter cake 2) 64.58g, to wherein adding 90mLDMF, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 3) 54.03g, filter residue (filter residue 3, i.e. thick carbazole) 18.03g.Get gained filter residue (filter residue 3) 8.85g, add the 16mL chlorobenzene, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 60 ℃ of filtrations obtain filter cake (filter cake 4) 5.99g, filter residue (filter residue 4) 2.56g.Get filter cake (filter cake 4) 5.68g, add the 27.5mL chlorobenzene, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 60 ℃ of filtrations obtain filter cake (filter cake 5) 5.04g, filter residue (filter residue 5) 0.56g.Add the 13.5mL chlorobenzene among gained filter cake (filter cake 5) 4.76g, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 6) 4.27g, filter residue (filter residue 6) 0.42g.Add the 12mL chlorobenzene among gained filter cake (filter cake 6) 2.01g, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 7) (being high-purity carbazole) 1.81g, filter residue (filter residue 7) 0.21g.Finally obtaining the carbazole product is the pale powder shape.From crude anthracene, do not carry out mother liquor and reclaim cyclical operation, the yield of carbazole is 42.23%, purity is 98.18%.
Annotate: in (1) example institute description process, if the quality sum of the filter cake of a certain washing process gained and corresponding filter residue greater than the raw materials quality of this process, reason is the solvent complete evaporate to dryness or be filtered dry in filter cake or the filter residue.
(2) above-mentioned carbazole yield is, the yield that washs each time products obtained therefrom is connected take advantage of, and the total recovery that obtains later on for seven times sees table 1 for details.Because the phenomenon that has all the time the incomplete evaporate to dryness of solvent or be filtered dry in measuring carbazole purity process is so use areas of peak normalization method further to calculate carbazole purity.Carbazole purity (1) in the table 1 refers to calculate with Internal standard curve method, carbazole purity (2) refers to calculate with areas of peak normalization method, and carbazole yield (1) refers to what the Mass Calculation according to carbazole purity (1) and each sample went out.
The carbazole yield calculates in table 1 example 1
* among the peak area normalization method result, the purity of front carbazole is lower than marker method, be because at this moment luxuriant and rich with fragrance content is high, and the content of carbazole is low, due to the response factor of carbazole is lower than the former.And the purity of back carbazole is higher than marker method, is when having removed solvent effect, and luxuriant and rich with fragrance content declines to a great extent, and major effect at this moment is anthracene, and the response factor of the anthracene reason lower than carbazole.Example 2 and 3 is same therewith.
For improving yield, reduce the loss of solvent and the loss of carbazole, can also the solvent that reclaims the filtrate merging that obtain wherein will be filtered behind above 4 chlorobenzene recrystallizations, chlorobenzene is used for the recrystallization of carbazole again, because the filter residue that obtains is less, can be used as raw material and mix with crude anthracene and turn back to dimethylbenzene and go the washing step of phenanthrene again to wash.
Example 2:
In the there-necked flask that agitator, reflux condensing tube and thermometer are housed, add 200g crude anthracene raw material, 150mL dimethylbenzene, under the agitation condition, be heated to 120 ℃ and make it dissolving, insulation 30min, be cooled to 60 ℃ of filtrations, obtain filter cake (filter cake 1) 120.65g, filter residue (filter residue 1) 72.93g; Repeat above-mentioned steps, add 240mL dimethylbenzene in gained filter cake (filter cake 1) 119.80g, under the agitation condition, 120 ℃ make it dissolving, insulation 30min, and 60 ℃ of filtrations obtain filter cake (filter cake 2) 101.25g, filter residue (filter residue 2) 17.91g; Add (filter cake 2) among gained filter cake (filter cake 2) 50.4g and enter 100mLDMF, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 3) 32.63g, filter residue (filter residue 3) 18.01g.Get gained filter residue (filter residue 3) 17.41g, add the 50mL chlorobenzene, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 40 ℃ of filtrations obtain filter cake (filter cake 4) 12.15g, filter residue (filter residue 4) 4.79g.Get filter cake (filter cake 4) 11.51g, add the 55mL chlorobenzene, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 60 ℃ of filtrations obtain filter cake (filter cake 5) 8.78g, filter residue (filter residue 5) 2.68g.Add the 24mL chlorobenzene among gained filter cake (filter cake 5) 8.41g, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 6) 7.6g, filter residue (filter residue 6) 0.78g.Add the 15mL chlorobenzene among gained filter cake (filter cake 6) 4.40g, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 7) (being high-purity carbazole) 3.94g, filter residue (filter residue 7) 0.42g.Finally obtaining the carbazole product is the pale powder shape.From crude anthracene, do not carry out mother liquor and reclaim cyclical operation, the yield of carbazole is 45.92%, purity is 97.39%.
Table 2 example 2 carbazole yields calculate
Example 3:
In the there-necked flask that agitator, reflux condensing tube and thermometer are housed, add 300g crude anthracene raw material, 240mL dimethylbenzene, under the agitation condition, be heated to 120 ℃ and make it dissolving, insulation 30min, 80 ℃ of filtrations obtain filter cake (filter cake 1) 200.51g, filter residue (filter residue 1) 93.83g; Repeat above-mentioned steps, add 280mL dimethylbenzene in gained filter cake (filter cake 1) 199g, under the agitation condition, 120 ℃ make it dissolving, insulation 30min, and 80 ℃ of filtrations obtain filter cake (filter cake 2) 158.13g, filter residue (filter residue 2) 37.41g; Add 60mLDMF among gained filter cake (filter cake 2) 52.5g, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 3) 33.3g, filter residue (filter residue 3) 19.38g.Get gained filter residue (filter residue 3) 9g, add the 40mL chlorobenzene, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 4) 5.49g, filter residue (filter residue 4) 3.30g.Get filter cake (filter cake 4) 5g, add the 17mL chlorobenzene, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 5) 3.87g, filter residue (filter residue 5) 1.20g.Add the 15mL chlorobenzene among gained filter cake (filter cake 5) 3.5g, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 6) 3.06g, filter residue (filter residue 6) 0.31g.Add the 7mL chlorobenzene among gained filter cake (filter cake 6) 2.7g, under the agitation condition, 100 ℃ make it dissolving, insulation 30min, and 30 ℃ of filtrations obtain filter cake (filter cake 7) (being high-purity carbazole) 2.24g, filter residue (filter residue 7) 0.38g.Finally obtaining the carbazole product is the pale powder shape.From crude anthracene, do not carry out mother liquor and reclaim cyclical operation, the yield of carbazole is 38.63%, purity is 97.93%.
Table 3 example 3 carbazole yields calculate
Embodiment 4:
With crude anthracene raw material among the embodiment 1 through twice xylene soluble crystallization, and the filter cake 3 that a DMF makes after dissolving crystallized is raw material, according to the dissolving crystallized same experiment condition of chlorobenzene among the embodiment 1, be dissolution with solvents crystal refining carbazole with chlorobenzene, dimethylbenzene and zellon respectively.Table 4 is the yield of the high purity carbazole for preparing with three kinds of dissolution with solvents crystallization processs respectively and the comparison of purity.
The comparison of table 4 chlorobenzene, dimethylbenzene and zellon refined carbazole
Notes: above yield is the single yield of each washing, and total recovery is that carbazole is through the total recovery (do not comprise and remove phenanthrene and take off the anthracene process, and do not carry out mother liquor and reclaim cyclical operation) of four washing process, the normalized result of purity employing peak area.
The result of table 4 shows, employings chlorobenzene is solvent, washs the carbazole successful and uses dimethylbenzene and zellon good, thick carbazole is through four washings, purity just can reach more than 98%, and the yield in each step is all more than 85%, and the total recovery of four washing carbazoles is 68.19%.And use dimethylbenzene or zellon, the yield of the first step is very low to be respectively about 58.15% and 61.05%, although second and third step yield is higher about 85%, but after washing through four, purity is the highest also can only to reach 87.13%, and the total recovery of washing carbazole in the click process is respectively 35.17% and 39.28%.
Claims (7)
1. a method for preparing the high purity carbazole specifically comprises the steps:
(1) take dimethylbenzene as the first solvent the crude anthracene raw material is carried out dissolving crystallized 2 times;
(2) take DMF as the second solvent carries out dissolving crystallized 1-2 time crystallized product obtained in the previous step, anthracene is separated with carbazole, obtain anthracene and thick carbazole;
(3) take chlorobenzene as the 3rd solvent the thick carbazole that made in the upper step is carried out dissolving crystallized 3-4 time, obtain the high purity carbazole, the solid-to-liquid ratio g/ml of thick carbazole and chlorobenzene is 1:2～1:5; Solvent temperature is 100 ℃; Tc is 30 ℃-60 ℃.
2. the method for preparing the high purity carbazole claimed in claim 1, wherein, the solid-to-liquid ratio g/ml of crude anthracene raw material and dimethylbenzene is 1:0.75-1:2 in the step (1), and solvent temperature is 120 ℃, and filtration temperature is 40-80 ℃.
3. the method for preparing the high purity carbazole claimed in claim 2, wherein, the solid-to-liquid ratio g/ml in the step (2) is 1: 1.2-1:2, solvent temperature is 100 ℃, filtration temperature is 30 ℃.
4. the method for preparing the high purity carbazole claimed in claim 1, wherein, the solid-to-liquid ratio g/ml of crude anthracene raw material and dimethylbenzene in the step (1) is 1: 1 for the first time, is 1: 1.5 for the second time, and solvent temperature is 120 ℃, and filtration temperature is 40 ℃.
5. the method for preparing the high purity carbazole claimed in claim 4, wherein, the solid-to-liquid ratio g/ml in the step (2) is 1:1.5, solvent temperature is 100 ℃; Tc is 30 ℃.
6. the method for preparing the high purity carbazole claimed in claim 1, wherein, the solid-to-liquid ratio g/ml of thick carbazole and chlorobenzene is 1:2-1:3 in the step (3), and solvent temperature is 100 ℃, and filtration temperature is 30 ℃.
7. the method for preparing the high purity carbazole claimed in claim 6 comprises, the crude anthracene raw material is dissolved in dimethylbenzene, and 120 ℃ of lower insulation 30min are cooled to 40 ℃ of filtrations, and filter cake repeats above-mentioned crystallisation process once; The gained filter cake dissolves in the DMF solvent, and 100 ℃ of lower insulation 30min are down to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and 100 ℃ of lower insulation 30min are down to 30 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, obtain the high purity carbazole.
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| CN105566031A (en) * | 2016-01-21 | 2016-05-11 | 太原理工大学 | Method for improving solvent selectivity |
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| CN103880732B (en) * | 2014-03-05 | 2016-06-08 | 上海鸿道节能环保科技发展有限公司 | A kind of method of purification of anthracene and carbazole |
| CN104193671B (en) * | 2014-08-22 | 2016-12-07 | 山西永东化工股份有限公司 | A kind of method of purification of coal tar naphtha carbazole |
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| CN105566031A (en) * | 2016-01-21 | 2016-05-11 | 太原理工大学 | Method for improving solvent selectivity |
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Application publication date: 20120229 Assignee: HUBEI HECHANG NEW MATERIAL TECHNOLOGY CO., LTD. Assignor: Taiyuan University of Technology Contract record no.: 2015420000097 Denomination of invention: Method for preparing carbazole Granted publication date: 20130130 License type: Exclusive License Record date: 20150610 |
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