CN102363608A - Method for preparing carbazole - Google Patents
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- CN102363608A CN102363608A CN2011103775573A CN201110377557A CN102363608A CN 102363608 A CN102363608 A CN 102363608A CN 2011103775573 A CN2011103775573 A CN 2011103775573A CN 201110377557 A CN201110377557 A CN 201110377557A CN 102363608 A CN102363608 A CN 102363608A
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Abstract
The invention relates to a method for preparing carbazole, in particular to a new 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 the novel method of from the crude anthracene raw material, extracting the high purity carbazole particularly.
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 advantage 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 bigger conjugated system and stronger intramolecularly electron transfer capacity, therefore has remarkable thermal property and photoelectric properties.In addition, carbazole is as biologically active substance, also is the focus of research like 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 the trend that rises year by year, to the purity requirement of carbazole also increasingly high (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 carbazole product gas purity, increase yield simultaneously as much as possible, 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 that the back that is heated is prone to coking, especially anthracene is big.The employing rectification method is produced, owing to need separated material be heated to boiling temperature, so energy consumption is very high, and the stage number that conventional distillation needs is very high, and equipment cost is big, needs to add nonvariant boiling reagent and adopts sequence of constant boiling and rectification could anthracene, phenanthrene and carbazole be separated.(2) the molten method of potassium: utilize the potassium fusant of carbazole to be insoluble to oils and to form sedimentary characteristics; With adding Ke Xingjia 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 YLENE recrystallization obtains high-purity carbazole.But this method will consume a large amount of alkali, and produces great amount of wastewater 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 big.
The solvent wash method is mainly still adopted in the production of domestic carbazole, and this method utilizes anthracene, phenanthrene, carbazole in certain solvent, to have different solubleness and separate, and can from crude anthracene, extract anthracene and carbazole.The shortcoming and defect of aforesaid method is: at first the crude anthracene dissolving being removed luxuriant and rich with fragrance process will wash 3-4 time; Separate anthracene and carbazole process and also will wash 2-3 time, when using benzene kind solvent to prepare pure carbazole, also need wash more than 7-8 time usually by thick carbazole; The process solvent wash tens times more than for preparing pure carbazole like this from crude anthracene; The product purity that obtains also is merely about 93%, 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 big, 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 Sino-Philippines removal efficient of whole technological process not high due to.Therefore, need 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.
The solid-to-liquid ratio of wherein 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) be that first solvent carries out dissolving crystallized 2 times the crude anthracene raw material with YLENE;
(2) be that the crystallized product that second solvent obtained a last step carries out dissolving crystallized 1-2 time with DMF, anthracene is separated with carbazole, obtain anthracene and thick carbazole;
(3) be that the 3rd solvent carries out dissolving crystallized 3-4 time the thick carbazole that made in the last step with chlorobenzene, obtain the high purity carbazole.
Thick carbazole refers to remove phenanthrene through YLENE, 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 through coal tar, and be the work in-process of coal tar processing, staple (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 YLENE 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 ℃.
The 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 an embodiment of the present invention, the solid-to-liquid ratio of crude anthracene raw material and YLENE 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 an 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 an 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 an embodiment of the present invention, the method for preparing the high purity carbazole comprises: the crude anthracene raw material is dissolved in YLENE, and 120 ℃ are incubated 30min down, 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 ℃ are incubated 30min down, reduce to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and 100 ℃ are incubated 30min down, reduce to 30 ℃ of-60 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, obtain the high purity carbazole.
In embodiment of the present invention, the method for preparing the high purity carbazole comprises: the crude anthracene raw material is dissolved in YLENE, and solid-to-liquid ratio is 1: 1; 120 ℃ are incubated 30min down; 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 ℃ are incubated 30min down, reduce to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and solid-to-liquid ratio is 1: 2, and 100 ℃ are incubated 30min down, reduce 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 embodiment of the present invention, the method for preparing the high purity carbazole comprises: the crude anthracene raw material is dissolved in YLENE, and 120 ℃ are incubated 30min down, 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 ℃ are incubated 30min down, reduce to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and 100 ℃ are incubated 30min down, reduce to 30 ℃ of-60 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, obtain the high purity carbazole.
In embodiment of the present invention, the method for preparing the high purity carbazole comprises: the crude anthracene raw material is dissolved in YLENE, and solid-to-liquid ratio is 1: 0.75; 120 ℃ are incubated 30min down; 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 ℃ are incubated 30min down, reduce to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and solid-to-liquid ratio is 1: 2, and 100 ℃ are incubated 30min down, reduce 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 embodiment of the present invention, the method for preparing the high purity carbazole comprises: the crude anthracene raw material is dissolved in YLENE, and 120 ℃ are incubated 30min down, 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 ℃ are incubated 30min down, reduce to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and 100 ℃ are incubated 30min down, reduce to 30 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, obtain the high purity carbazole.
In embodiment of the present invention, the method for preparing the high purity carbazole comprises: crude anthracene is dissolved in YLENE, and solid-to-liquid ratio is 1: 1.2; 120 ℃ are incubated 30min down; 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 ℃ are incubated 30min down, reduce to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and solid-to-liquid ratio is 1: 3, and 100 ℃ are incubated 30min down, reduce 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 " is meant, the ratio of solid and liquid, and wherein solid adopts MU gram meter, and liquid adopts volume unit milliliter meter.
Adopt two steps of YLENE to remove phenanthrene among the present invention, make luxuriant and rich with fragrance decreasing ratio, reduced luxuriant and rich with fragrance influence greatly the carbazole washing process more than 90%; 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%), and the yield of washing click process carbazole is 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 utilization again of solvent and do not influence 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 the solid-to-liquid ratio of broad (1: 1-5) and under the filtration temperature (30-60 ℃), can both guarantee washing effect, easy handling.
Embodiment
Specific embodiment of the present invention is for better explanation content of the present invention, and does 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%, mark calibration curve method result in the carbazole 15.97%).
Adopting the method for gas chromatography determination carbazole content is interior mark calibration curve method and peak area normalization method dual mode, and actual conditions is following:
Shellomadzu (day island proper Tianjin) GC 2014;
-5 (USA) capillary column (0.32mm x 30m); Stationary phase is 5% phenylbenzene/95% dimethyl polysiloxane, and 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, are raised to 200 ℃ with 3.5 ℃/min then, keep 1min again, are raised to 250 ℃ with 10 ℃/min at last.With the 9-Fluorenone be internal standard substance content greater than 99%, carbazole standard specimen content is greater than 99.3%, acetonitrile (HPLC) is the dissolution with solvents sample, the mark calibration curve method carries out chromatogram quantification in adopting.Get 5 experimental points when measuring graticule, carbazole is marked liquid concentration be diluted to 1.4mg/mL, 1.0mg/mL, 0.6mg/mL, 0.2mg/mL, 0.05mg/mL respectively; The 9-Fluorenone is diluted to 0.6mg/mL, and remains unchanged.Respectively these five carbazole standard models are measured under above-mentioned GC condition; With the sample concentration is 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 an ordinate zou; Draw mark typical curve in the carbazole, it is following to obtain marking the typical curve equation in the carbazole through linear match: 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 article still is 0.6mg/mL, under same chromatographic condition, measures, and draws Ai/As, and substitution formula (1) calculates and gets final product.
Owing to all can contain certain amount of solvent in the sample that each step obtains, for fear of the influence of solvent, so yield is marked calibration curve method (on same benchmark, calculating) in adopting when calculating.And it is same because the influence of solvent; The final purity of carbazole that the mark calibration curve method obtains in adopting 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.
Instance 1:
In the there-necked flask that whisking appliance, reflux condensing tube and TM are housed, add 300g crude anthracene raw material, 300mL YLENE, 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 YLENE, 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, promptly 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) instance institute description process, the quality sum of the filter cake of a certain washing process gained and corresponding filter residue is as if the raw materials quality greater than this process, and reason is that complete evaporate to dryness of the solvent in filter cake or the filter residue or filter are done.
(2) above-mentioned carbazole yield does, connects the yield that washs products obtained therefrom each time and takes advantage of, and the total recovery that obtains later on for seven times sees table 1 for details.Because the phenomenon that in measuring carbazole purity process, exists incomplete evaporate to dryness of solvent or filter to do all the time is so use the peak area normalization method further to calculate carbazole purity.Carbazole purity (1) in the table 1 is meant with interior mark calibration curve method and calculates, and carbazole purity (2) is meant with the peak area normalization method and calculates, and carbazole yield (1) is meant what the Mass Calculation according to carbazole purity (1) and each sample went out.
The carbazole yield calculates in table 1 instance 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, the response factor of carbazole than the former low due to.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 main influence at this moment is anthracene, and the response factor of the anthracene reason lower than carbazole.Instance 2 and 3 therewith together.
For improving yield; Reduce the loss of solvent and the loss of carbazole; Can also the filtrating merging that above 4 chlorobenzene recrystallization after-filtration obtain be reclaimed solvent wherein; Chlorobenzene is used for the recrystallization of carbazole once more, because the filter residue that obtains is less, can be used as raw material and mixes with crude anthracene and turn back to YLENE and go the washing step of phenanthrene to wash once more.
Instance 2:
In the there-necked flask that whisking appliance, reflux condensing tube and TM are housed, add 200g crude anthracene raw material, 150mL YLENE, 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, in gained filter cake (filter cake 1) 119.80g, add 240mL YLENE, 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 go into 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 instance 2 carbazole yields calculate
Instance 3:
In the there-necked flask that whisking appliance, reflux condensing tube and TM are housed, add 300g crude anthracene raw material, 240mL YLENE, 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, in gained filter cake (filter cake 1) 199g, add 280mL YLENE, 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 instance 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, use chlorobenzene, YLENE and zellon to be dissolution with solvents crystal refining carbazole 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, YLENE and zellon refined carbazole
Annotate: above yield is the single yield of each washing, and total recovery is the total recovery (do not comprise remove phenanthrene and take off anthracene process, and do not carry out mother liquor reclaim cyclical operation) of carbazole through four washing process, and purity adopts the normalized result of peak area.
The result of table 4 shows that the employing chlorobenzene is a solvent, and washing carbazole effect obviously uses YLENE 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 YLENE or zellon; The yield of the first step is very low to be respectively about 58.15% and 61.05%; Though 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 (10)
1. method for preparing the high purity carbazole comprises thick carbazole dissolving crystallized step in chlorobenzene.
2. the described method for preparing the high purity carbazole of claim 1, the solid-to-liquid ratio of wherein thick carbazole and chlorobenzene is 1: 2～1: 5, and solvent temperature is 100 ℃, and Tc is 30 ℃-60 ℃.
3. claim 1 or the 2 described methods that prepare the high purity carbazole specifically comprise the steps:
(1) be that first solvent carries out dissolving crystallized 2 times the crude anthracene raw material with YLENE;
(2) be that the crystallized product that second solvent obtained a last step carries out dissolving crystallized 1-2 time with DMF, anthracene is separated with carbazole, obtain anthracene and thick carbazole;
(3) be that the 3rd solvent carries out dissolving crystallized 3-4 time the thick carbazole that made in the last step with chlorobenzene, obtain the high purity carbazole.
4. the described method for preparing the high purity carbazole of claim 3, wherein, the solid-to-liquid ratio of crude anthracene raw material and YLENE is 1 in the step (1): 0.75-1: 2, solvent temperature is 120 ℃, filtration temperature is 40-80 ℃.
5. the described method for preparing the high purity carbazole of claim 4, wherein, the solid-to-liquid ratio in the step (2) is 1: 1.2-1: 2, solvent temperature is 100 ℃, filtration temperature is 30 ℃.
6. the described method for preparing the high purity carbazole of claim 5, wherein, the 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 ℃.
7. the described method for preparing the high purity carbazole of claim 6, wherein, the solid-to-liquid ratio of crude anthracene raw material and YLENE is 1: 1 for the first time in the step (1), and be 1: 1.5 the second time, and solvent temperature is 120 ℃, and filtration temperature is 40 ℃.
8. the described method for preparing the high purity carbazole of claim 7, wherein, the solid-to-liquid ratio in the step (2) is 1: 1.5, solvent temperature is 100 ℃; Tc is 30 ℃.
9. the described method for preparing the high purity carbazole of claim 8, wherein, the solid-to-liquid ratio of crude anthracene raw material and chlorobenzene is 1 in the step (3): 2-1: 3, solvent temperature is 100 ℃, filtration temperature is 30 ℃.
10. the described method for preparing the high purity carbazole of claim 9 comprises, the crude anthracene raw material is dissolved in YLENE, and 120 ℃ are incubated 30min down, 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 ℃ are incubated 30min down, reduce to 30 ℃ of filtrations; The gained filter residue dissolves in chlorobenzene, and 100 ℃ are incubated 30min down, reduce to 30 ℃ of-60 ℃ of filtrations; Repeat above-mentioned chlorobenzene crystallisation process 3 times, obtain the high purity carbazole.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103880732A (en) * | 2014-03-05 | 2014-06-25 | 上海鸿道节能环保科技发展有限公司 | Refined anthracene and carbazole purification method |
| CN104193671A (en) * | 2014-08-22 | 2014-12-10 | 山西永东化工股份有限公司 | Purification method of coal tar fine carbazole |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566031A (en) * | 2016-01-21 | 2016-05-11 | 太原理工大学 | Method for improving solvent selectivity |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880732A (en) * | 2014-03-05 | 2014-06-25 | 上海鸿道节能环保科技发展有限公司 | Refined anthracene and carbazole purification method |
| 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 |
| CN104193671A (en) * | 2014-08-22 | 2014-12-10 | 山西永东化工股份有限公司 | Purification method of coal tar fine 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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| CN102363608B (en) | 2013-01-30 |
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