CN103382148B - Industrial fluorene production process - Google Patents
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- CN103382148B CN103382148B CN201310316385.8A CN201310316385A CN103382148B CN 103382148 B CN103382148 B CN 103382148B CN 201310316385 A CN201310316385 A CN 201310316385A CN 103382148 B CN103382148 B CN 103382148B
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Abstract
The invention belongs to the field of chemical engineering and particularly relates to an industrial fluorene production process. The process solves the technical problem that the existing production process is large in power consumption and fluorene resource waste, low in fluorene product purity and high in production cost. The industrial fluorene production process includes the following steps that a. heavy wash oil is pre-crystallized and pre-crystallized solid products are obtained; b. the pre-crystallized solid products are distilled at intervals, and main distillate fraction of fluorene is extracted; c. the main distillate fraction of fluorene is crystallized and centrifuged to obtain industrial fluorene products. The novel process reduces energy consumption for producing industrial fluorene, effectively reduces fluorene resource waste and saves production cost.
Description
Technical field
The invention belongs to chemical field, be specifically related to the production technique of Industrial fluorene.
Technical background
Fluorenes, be a kind of important organic synthesis raw material, the fluorenes content in coal tar is about 1.0 ~ 2.0%, and fluorenes product is mainly from the wash oil fraction (i.e. heavy wash oil or industrial acenaphthylene Residual oil, containing fluorenes about 25 ~ 35%) in coal tar distillation process.Fluorenes can be used for system medicine (manufacturing spasmolytic, tranquilizer, anodyne, hypotensor), dyestuff (replacing anthraquinone synthesis indanthrene dye); All right synthetic pesticide, weedicide; Shock resistance synthetic glass processed and fluorenes urea formaldehyde; Also can be used as wetting agent, washing composition, flash liquid agent, sterilizing agent etc.Can be made into trinitro-fluorenone, for xerox; Also can be used for synthesizing aryl transparent nylon.
" from heavy wash oil, extracting the technical study of Industrial fluorene " discloses a kind of method extracting Industrial fluorene from heavy wash oil, the steps include: that heavy wash oil is raw material, batch distillation is carried out by high efficiency packing tower, cut the fluorenes main distillate fraction being greater than 60% containing fluorenes, fluorenes main distillate fraction and a certain proportion of dimethylbenzene are mixed in heating kettle and heat, decrease temperature crystalline after fine melt, is separated fluorenes crystallisate and dimethylbenzene Residual oil by strainer, whizzer; The front-end volatiles of batch distillation, residue return joins heavy wash oil raw material, to reclaim fluorenes resource wherein.But there is following shortcoming in aforesaid method: (1) is improve the concentration degree of fluorenes at fluorenes main distillate fraction, when fluorenes front-end volatiles are greater than 50% containing fluorenes, need carry out total reflux 4 hours, then with high reflux ratio (less produced quantity, larger quantity of reflux) excessively to fluorenes main distillate fraction.Therefore, the huge waste cut causing the still-process energy of front-end volatiles; (2) fluorenes main distillate fraction is containing fluorenes only more than 60%, is purified by a large amount of xylene solvent of consumption, washes away impurity wherein; (3) the fluorenes product purity obtained is not high, is 92 ~ 93%.
" from acenaphthene oil, extracting the research of fluorenes " also discloses a kind of method extracting fluorenes from acenaphthene oil, its preparation process is: with the wash oil fraction of coal tar distillation for raw material, adopt decompression batch distillation to cut fluorenes cut, fluorenes cut through washing, the crystallization of benzene kind solvent, obtains fluorenes product again.There is following shortcoming in the method: the requirement of (1) underpressure distillation to equipment is higher, increases facility investment and operation easier; (2) fluorenes main distillate fraction is containing fluorenes only more than 60%, is purified by a large amount of xylene solvent of consumption, washes away impurity wherein; (3) the fluorenes product purity that obtains of fluorenes cut crystallization is not high, is only 90%.
" with heavy wash oil highly industry fluorenes " discloses a kind of method of heavy wash oil highly industry fluorenes, the steps include: with the wash oil fraction of coal tar distillation as raw material, batch distillation cuts fluorenes main distillate fraction, fluorenes main distillate fraction uses dimethylbenzene washing, crystallization, obtain 93% Industrial fluorene product, again with dimethylbenzene washing, crystallization, obtain 95% Industrial fluorene product.The shortcoming of the method has: the fluorenes main distillate fraction cut is too high containing fluorenes, about 75%, cause that the temperature range cutting fluorenes main distillate fraction is little, distillate output is low, fluorenes main distillate fraction only has 20% to washing oil raw material yield, cause a large amount of fluorenes resources loss in other cuts, for reclaiming fluorenes resource, other cuts being returned and joins raw material washing oil and heavily steam, causing the waste of the energy.
Original production technique of fluorenes is: by wash oil fraction batch distillation, cuts the fluorenes main distillate fraction containing fluorenes about 60%, then fluorenes main distillate fraction is dissolved in benzene kind solvent, decrease temperature crystalline, obtain Industrial fluorene product.For ensureing fluorenes product yield, the fluorenes product purity that primary solvent crystallization obtains can only reach about 90%, and for improving the quality of products, usually need to carry out secondary solvent wash crystallization, Industrial fluorene purity can reach more than 95%.Simultaneously for reclaiming the fluorenes resource in batch distillation process in other cut, part cut (containing fluorenes more than 25%) need be returned wash oil fraction, heavily steaming as lower whorl batch distillation raw material.But the following shortcoming of existing production technique: (1) only has 25 ~ 35% due to fluorenes content in wash oil fraction, therefore will a large amount of front-end volatiles, dibenzofuran cut, fluorenes front-end volatiles, fluorenes after cut, Residual oil etc. be produced in batch distillation process, the flow process of distillation is longer, needs to consume a large amount of energy; (2) be unfavorable for fluorenes resource concentrating in fluorenes main distillate fraction, a large amount of fluorenes resources loss, in dibenzofuran cut, fluorenes front-end volatiles, fluorenes after cut and Residual oil, causes the waste of resource; (3) fluorenes main distillate fraction generally only has an appointment 60% containing fluorenes, and therefore from fluorenes main distillate fraction, purifying industrial fluorenes needs to consume a large amount of solvents, and is unfavorable for obtaining highly purified fluorenes product.
Summary of the invention
Technical problem to be solved by this invention is that existing energy consumption in production process is large, the waste of fluorenes resource is large, fluorenes product purity is not high, production cost is high.
The technical scheme that the present invention solves the problems of the technologies described above is to provide a kind of production technique of Industrial fluorene, and its step comprises: a, heavy wash oil are pre-crystallized, obtains pre-crystallized solid product;
B, pre-crystallized solid product is carried out batch distillation, cut fluorenes main distillate fraction;
C, fluorenes main distillate fraction through crystallization, centrifugally obtain Industrial fluorene product.
Wherein, in the production technique of above-mentioned Industrial fluorene, the pre-crystallized step of heavy wash oil described in step a comprises: first in heavy wash oil, add coking mixed solvent, is heated to 85 DEG C ~ 115 DEG C, stirs; Again said mixture is cooled to 65 ~ 85 DEG C, then gradient cooling to 30 ~ 38 DEG C; Pre-crystallized solid product is obtained finally by centrifugal.
Preferably, described coking mixed solvent is the mixed solvent of dimethylbenzene and toluene.
Preferred further, the volume ratio of described dimethylbenzene and toluene is 1:0 ~ 2:1.
Preferably, the volume ratio of described coking mixed solvent and heavy wash oil is 1 ︰ 5 ~ 1 ︰ 7.
Preferably, the speed of described gradient cooling is 1 ~ 5 DEG C/h.
Wherein, in the production technique of above-mentioned Industrial fluorene, the batch distillation described in step b cuts front-end volatiles before 280 DEG C, and 280 DEG C ~ 285 DEG C cut dibenzofuran cut, and 285 DEG C ~ 292 DEG C cut fluorenes main distillate fraction, cuts fluorenes after cut extremely without cut extraction after 292 DEG C.
Preferably, described dibenzofuran cut can carry out batch distillation with fluorenes after cut together with pre-crystallized solid product next time.
Wherein, in the production technique of above-mentioned Industrial fluorene, crystallization described in step c is twice crystallization, concrete steps comprise: (1) primary crystallization, fluorenes main distillate fraction and secondary crystal mother liquor by volume 1:0.6 ~ 1:1.4 mix, and heat, be stirred to and dissolve completely, Temperature fall is to occurring crystal seed, be cooled to 28 ~ 36 DEG C with the velocity gradient of 1 ~ 5 DEG C/h again, filter and obtain primary crystallization product; (2) secondary crystal, primary crystallization product and dimethylbenzene by volume 1:0.6 ~ 1:1.4 mix, and heating, stir and make it dissolve, and Temperature fall to occurring crystal seed, then is cooled to 28 ~ 34 DEG C with the velocity gradient of 1 ~ 4 DEG C/h, centrifugally obtains Industrial fluorene product.
Beneficial effect of the present invention is: in the production technique of Industrial fluorene provided by the invention, heavy wash oil is through pre-crystallized, the materials such as a large amount of light constituents (are mainly acenaphthene, dibenzofuran etc.) be removed, do not enter distillation process, decrease the distillation amount of heavy wash oil, if the energy consumption of former technique still-process is decided to be 100%, the heavy wash oil that then art breading provided by the invention is identical, distillation process energy consumption can reduce by more than 40%, pre-crystallized process energy consumption is few simultaneously, the pre-crystallized process energy consumption of 5%(being about distillation process energy consumption is the water circulating pump of crystallizer and the electric energy of whizzer consumption, the electricity consumption time is short, and distillation process is highly energy-consuming operation, energy consumption comprises: raw material, the conveying of cut, heat holding temperature at the bottom of still about 400 DEG C, the condensing reflux of tower top, and contrast pre-crystallized operation, the still-process time is much longer), therefore, process the heavy wash oil of identical amount, the more original technique of technique total energy consumption provided by the invention can reduce by more than 35%.Because a large amount of impurity is removed in pre-crystallized process, the impure fraction amounts such as the front-end volatiles that still-process is obtained, dibenzofuran cut obviously reduce, distillation boiling range shortens, the fluorenes stock number be lost in impure fraction obviously reduces, the concentration degree of fluorenes resource in fluorenes main distillate fraction can reach more than 70%, effectively reduces the loss of fluorenes resource in still-process.Adopt production technique provided by the invention, the fluorenes main distillate fraction obtained is higher containing fluorenes, reaches 65% ~ 75%, greatly reduces the usage quantity of purification solvent and the energy consumption of solvent reclamation process, be conducive to the Industrial fluorene product producing high-content simultaneously.Adopt the purity of method for producing industrial fluorenes of the present invention to be more than 95%, according to quality product requirement, by the operation of adjustment fluorenes main distillate fraction solvent crystallization, obtain the smart fluorenes that purity is greater than 97%.The production technique of Industrial fluorene provided by the invention, greatly reduces energy consumption, has saved production cost, effectively reduces the waste of fluorenes resource.
Accompanying drawing explanation
The production technological process of Fig. 1 Industrial fluorene provided by the invention.Wherein, " new washing oil " is for the production of methylnaphthalene, lightweight washing oil, industrial acenaphthylene; " carbolineum " can be used for producing crude anthracene or allocating mixing carbolineum into, takes out with the form of asphaltum oil and carbon black oil.
The crystallization processes schema of Fig. 2 step c of the present invention.
The production technique of the former technique of Fig. 3 and Industrial fluorene provided by the invention the comparing of each cut quality after distillation.
In the production technique fluorenes cut of the former technique of Fig. 4 and Industrial fluorene provided by the invention and fluorenes product, fluorenes content compares.
The distribution of fluorenes in each cut in the production technique of the former technique of Fig. 5 and Industrial fluorene provided by the invention.
Embodiment
The step of the production technique of Industrial fluorene comprises:
A, heavy wash oil are pre-crystallized: first in heavy wash oil, add coking mixed solvent, heating, stirring, and the crystallisate in heavy wash oil is dissolved completely, and temperature is 85 DEG C ~ 115 DEG C; Extremely just have crystallisate to separate out said mixture Temperature fall again, temperature range is 65 ~ 85 DEG C, then is cooled to 28 ~ 38 DEG C with the velocity gradient of 1 ~ 5 DEG C/h; Be separated finally by whizzer and obtain pre-crystallized solid product; Wherein, coking mixed solvent and heavy wash oil ratio 1 ︰ 5 ~ 1 ︰ 7.
B, pre-crystallized product is carried out batch distillation, cut fluorenes main distillate fraction: before 280 DEG C, cut front-end volatiles, 280 DEG C ~ 285 DEG C cut dibenzofuran cut, and 285 DEG C ~ 292 DEG C cut fluorenes main distillate fraction, cut fluorenes after cut to without cut extraction after 292 DEG C;
C, fluorenes main distillate fraction through crystallization, centrifugally obtain Industrial fluorene product.
Wherein, in the step a of the production technique of above-mentioned Industrial fluorene, described coking mixed solvent is the mixed solvent of dimethylbenzene and toluene.
Wherein, in the step a of the production technique of above-mentioned Industrial fluorene, the volume ratio of described dimethylbenzene and toluene is 1:0 ~ 2:1.
Wherein, in the step b of the production technique of above-mentioned Industrial fluorene, described dibenzofuran cut can carry out batch distillation with fluorenes after cut together with pre-crystallized solid product next time, thus reduces the loss of fluorenes resource in still-process further, saves production cost.
Wherein, in the step c of the production technique of above-mentioned Industrial fluorene, described crystallization is twice crystallization, concrete steps comprise: (1) primary crystallization, and fluorenes main distillate fraction and secondary crystal mother liquor by volume 1:0.6 ~ 1:1.4 mix, and heat, be stirred to and dissolve completely, Temperature fall is to occurring crystal seed, be cooled to 28 ~ 36 DEG C with the velocity gradient of 1 ~ 5 DEG C/h again, filter and obtain primary crystallization product, purity is 89 ~ 93%; (2) secondary crystal, primary crystallization product and novel solvent (dimethylbenzene) by volume 1:0.6 ~ 1:1.4 mix, and heating, stirring make it dissolve, Temperature fall is to occurring crystal seed, be cooled to 28 ~ 34 DEG C with the velocity gradient of 1 ~ 4 DEG C/h again, centrifugally obtain Industrial fluorene product, purity is greater than 96%.
The secondary crystal mother liquor obtained is the saturated mother liquor of fluorenes, and impurity is less, then it is mixed with fluorenes main distillate fraction, melts, and carries out primary crystallization, so both can reduce the consumption of novel solvent, can improve primary crystallization yield again.
Wherein, principle pre-crystallized described in the production technique of above-mentioned Industrial fluorene is: because the solubleness of fluorenes in coking mixed solvent is less than other impurity (acenaphthene, dibenzofuran, methyl dibenzofuran), therefore, in pre-crystallized process, a large amount of impurity, by the light constituent that is dissolved in solvent and washing oil raw material, does not form crystallisate.Simultaneously because coking mixed solvent and heavy wash oil volume ratio are 1 ︰ 5 ~ 1 ︰ 7, the ratio of coking mixed solvent is less, and fluorenes solubleness is in a solvent less, therefore in gradient cooling process, most fluorenes will enter crystallisate, and the fluorenes be lost in mother liquor is less.In the crystallisate formed, fluorenes content can reach 45% ~ 50%.
Embodiment 1
A, heavy wash oil are pre-crystallized: first in 1800g heavy wash oil (containing fluorenes 32.2%), add dimethylbenzene 300mL, be heated to 90 DEG C, stir, the crystallisate in heavy wash oil is dissolved completely; Again by said mixture Temperature fall to 70 DEG C, then be cooled to 35 DEG C with the velocity gradient of 3 DEG C/h; Last suction filtration obtains pre-crystallized solid product 1012g, containing fluorenes 48.8%;
B, by the distillation dibenzofuran cut of pre-crystallized solid product 1012g and last time, fluorenes after cut altogether 288g(containing fluorenes 32%), carry out batch distillation, front-end volatiles are cut before 280 DEG C, 280 DEG C ~ 285 DEG C cut dibenzofuran cut, 285 DEG C ~ 292 DEG C cut fluorenes main distillate fraction 570g, containing fluorenes 73.4%, cut fluorenes after cut after 292 DEG C extremely without cut extraction;
C, primary crystallization: fluorenes main distillate fraction 570g mixes with secondary crystal mother liquor 500mL, heat 75 DEG C, be stirred to and dissolve completely, Temperature fall to 60 DEG C, then be cooled to 34 DEG C with the velocity gradient of 2 DEG C/h, and filter and obtain primary crystallization product 388g, purity is 91.5%.
Secondary crystal: primary crystallization product 388g mixes with dimethylbenzene 280mL, heat 85 DEG C, stir make it dissolve, Temperature fall to 70 DEG C, 30 DEG C are cooled to again with the velocity gradient of 2 DEG C/h, suction filtration obtains Industrial fluorene product 302g, purity 97.2%, is 50.6% to fluorenes resource recovery in heavy wash oil.
Embodiment 2
A, heavy wash oil are pre-crystallized: first in 1800g heavy wash oil (containing fluorenes 33.0%), add dimethylbenzene 350mL, be heated to 90 DEG C, stir, the crystallisate in heavy wash oil is dissolved completely; Again by said mixture Temperature fall to 70 DEG C, then be cooled to 34 DEG C with the velocity gradient of 3 DEG C/h; Last suction filtration obtains pre-crystallized solid product 945g, containing fluorenes 52.2%;
B, by pre-crystallized solid product 945g and last distillation dibenzofuran cut, fluorenes after cut altogether 295g(containing fluorenes 30.2%), carry out batch distillation, front-end volatiles are cut before 280 DEG C, 280 DEG C ~ 285 DEG C cut dibenzofuran cut, 285 DEG C ~ 292 DEG C cut fluorenes main distillate fraction 586g, containing fluorenes 72.5%, cut fluorenes after cut after 292 DEG C extremely without cut extraction;
C, primary crystallization: fluorenes main distillate fraction 586g mixes with secondary crystal mother liquor 500mL, heat 75 DEG C, be stirred to and dissolve completely, Temperature fall to 60 DEG C, then be cooled to 36 DEG C with the velocity gradient of 2 DEG C/h, and filter and obtain primary crystallization product 387g, purity is 92.1%.
Secondary crystal: primary crystallization product 387g mixes with dimethylbenzene 280mL, heat 85 DEG C, stir make it dissolve, Temperature fall to 70 DEG C, 32 DEG C are cooled to again with the velocity gradient of 2 DEG C/h, suction filtration obtains Industrial fluorene product 290g, purity 97.6%, to the fluorenes rate of recovery 47.6% in heavy wash oil.
Embodiment 3
A, heavy wash oil are pre-crystallized: first in 1800g heavy wash oil (containing fluorenes 30.8%), add dimethylbenzene 260mL, be heated to 90 DEG C, stir, the crystallisate in heavy wash oil is dissolved completely; Again by said mixture Temperature fall to 70 DEG C, then be cooled to 37 DEG C with the velocity gradient of 5 DEG C/h; Last suction filtration obtains pre-crystallized solid product 1029g, containing fluorenes 45.2%;
B, by pre-crystallized solid product 1029g and last distillation dibenzofuran cut, fluorenes after cut altogether 290g(containing fluorenes 30.4%), carry out batch distillation, front-end volatiles are cut before 280 DEG C, 280 DEG C ~ 285 DEG C cut dibenzofuran cut, 285 DEG C ~ 292 DEG C cut fluorenes main distillate fraction 568g, containing fluorenes 68.2%, cut fluorenes after cut after 292 DEG C extremely without cut extraction;
C, primary crystallization: fluorenes main distillate fraction 568g mixes with secondary crystal mother liquor 500mL, heat 75 DEG C, be stirred to and dissolve completely, Temperature fall to 60 DEG C, then be cooled to 35 DEG C with the velocity gradient of 2 DEG C/h, and filter and obtain primary crystallization product 359g, purity is 90.5%.
Secondary crystal: primary crystallization product 359g mixes with dimethylbenzene 280mL, heat 85 DEG C, stir make it dissolve, Temperature fall to 70 DEG C, 32 DEG C are cooled to again with the velocity gradient of 2 DEG C/h, suction filtration obtains Industrial fluorene product 268g, purity 96.8%, to the fluorenes rate of recovery 46.8% in heavy wash oil.
Embodiment 4
A, heavy wash oil are pre-crystallized: first in 1800g heavy wash oil (containing fluorenes 32.8%), add dimethylbenzene 250mL, toluene 50mL, be heated to 95 DEG C, stir, the crystallisate in heavy wash oil is dissolved completely; Again by said mixture Temperature fall to 70 DEG C, then be cooled to 32 DEG C with the velocity gradient of 1 DEG C/h; Last suction filtration obtains pre-crystallized solid product 1074g, containing fluorenes 47.4%;
B, by pre-crystallized solid product 1074g and last distillation dibenzofuran cut, fluorenes after cut altogether 287g(containing fluorenes 30.0%), carry out batch distillation, front-end volatiles are cut before 280 DEG C, 280 DEG C ~ 285 DEG C cut dibenzofuran cut, 285 DEG C ~ 292 DEG C cut fluorenes main distillate fraction 592g, containing 70.5%, cut fluorenes after cut after 292 DEG C extremely without cut extraction;
C, primary crystallization: fluorenes main distillate fraction 592g mixes with secondary crystal mother liquor 500mL, heat 75 DEG C, be stirred to and dissolve completely, Temperature fall to 60 DEG C, then be cooled to 34 DEG C with the velocity gradient of 2 DEG C/h, and filter and obtain primary crystallization product 392g, purity is 91.3%.
Secondary crystal: primary crystallization product 392g mixes with dimethylbenzene 330mL, heat 85 DEG C, stir make it dissolve, Temperature fall to 70 DEG C, 30 DEG C are cooled to again with the velocity gradient of 2 DEG C/h, suction filtration obtains Industrial fluorene product 309g, purity 97.5%, to the fluorenes rate of recovery 51.0% in heavy wash oil.
Embodiment 5
A, heavy wash oil are pre-crystallized: first in 1800g heavy wash oil (containing fluorenes 32.0%), add dimethylbenzene 200mL, toluene 100mL, be heated to 95 DEG C, stir, the crystallisate in heavy wash oil is dissolved completely; Again by said mixture Temperature fall to 70 DEG C, then be cooled to 32 DEG C with the velocity gradient of 5 DEG C/h; Last suction filtration obtains pre-crystallized solid product 1028g, containing fluorenes 47.6%;
B, by pre-crystallized solid product 1028g and last distillation dibenzofuran cut, fluorenes after cut altogether 262g(containing fluorenes 33%), carry out batch distillation, front-end volatiles are cut before 280 DEG C, 280 DEG C ~ 285 DEG C cut dibenzofuran cut, 285 DEG C ~ 292 DEG C cut fluorenes main distillate fraction 584g, containing 71.1%, cut fluorenes after cut after 292 DEG C extremely without cut extraction;
C, primary crystallization: fluorenes main distillate fraction 584g mixes with secondary crystal mother liquor 500mL, heat 75 DEG C, be stirred to and dissolve completely, Temperature fall to 60 DEG C, then be cooled to 34 DEG C with the velocity gradient of 2 DEG C/h, and filter and obtain primary crystallization product 381g, purity is 91.8%.
Secondary crystal: primary crystallization product 381g mixes with dimethylbenzene 330mL, heat 85 DEG C, stir make it dissolve, Temperature fall to 70 DEG C, 32 DEG C are cooled to again with the velocity gradient of 2 DEG C/h, suction filtration obtains Industrial fluorene product 288g, purity 97.0%, to the fluorenes rate of recovery 48.6% in heavy wash oil.
Embodiment 6 does not have the effect comparison when technique of pre-crystallized process and art breading same materials of the present invention
(1) distillation amount and energy consumption comparison
Drawn by table 1, in the production technique of Industrial fluorene provided by the invention, heavy wash oil is through pre-crystallized, and the impurity such as a large amount of light constituents are removed, and does not enter Distallation systm, decreases the distillation amount of heavy wash oil.If will the distillation process energy consumption of the technique of pre-crystallized process do not had to be decided to be 100%, then the heavy wash oil that art breading provided by the invention is identical, distillation process energy consumption reduces 45%(distillation energy consumption ratio and is similar to distillating material amount ratio).
Distillation amount and energy consumption comparison when table 1 does not have the technique of pre-crystallized process and an art breading same materials amount of the present invention
" last cut " in table 1 is the dibenzofuran cut that obtains in last batch distillation process and fluorenes after cut, and in this part cut, fluorenes content is greater than 25%, needs back to be fitted on epicycle distillation, to reclaim fluorenes resource wherein; The raw material that " epicycle raw material " is epicycle batch distillation; " actual distillation amount " is last cut and epicycle raw material sum.
Meanwhile, in pre-crystallized product, the impurity such as light constituent is less, and the front-end volatiles formed in batch distillation process obviously reduce, and reduces still-process energy consumption further, sees Fig. 3.Wherein, each cut quality " not having pre-crystallized technique " in Fig. 3 for batch distillation 640g heavy wash oil obtains, each cut quality that the pre-crystallized product that " technique of the present invention " is batch distillation 550g obtains.
(2) fluorenes content balance
As can be seen from Figure 4, in the production technique of Industrial fluorene provided by the invention, fluorenes main distillate fraction is higher containing fluorenes, reaches 65% ~ 75%, greatly reduces the usage quantity of purification solvent, and the energy consumption of solvent reclamation process, is conducive to the Industrial fluorene product producing high-content simultaneously.
(3) profiles versus of fluorenes in each cut
As can be seen from Figure 5, in the production technique of Industrial fluorene provided by the invention, the concentration degree of fluorenes resource in fluorenes cut improves greatly.Do not have in the still-process of pre-crystallized process, in fluorenes cut, fluorenes resource only accounts for 56% of fluorenes total amount, and other fluorenes resources losses are in front-end volatiles (about 5%), dibenzofuran cut (about 30%), fluorenes after cut and Residual oil (about 10%).After increasing pre-crystallized technique, the fluorenes resource in dibenzofuran cut, fluorenes after cut obviously lowers, and the concentration degree of fluorenes resource in fluorenes main distillate fraction can reach more than 70%, effectively reduces the loss of fluorenes resource.
Above-described embodiment can draw, the production technique of Industrial fluorene provided by the invention greatly reduces energy consumption, has saved production cost, effectively reduces the wave of fluorenes resource.
Claims (2)
1. the production technique of Industrial fluorene, is characterized in that: this production craft step comprises:
A, heavy wash oil are pre-crystallized, obtain pre-crystallized solid product; The pre-crystallized step of described heavy wash oil comprises: first in heavy wash oil, add coking mixed solvent, is heated to 85 DEG C ~ 115 DEG C, stirs; Again said mixture is cooled to 65 ~ 85 DEG C, then gradient cooling to 30 ~ 38 DEG C; Pre-crystallized solid product is obtained finally by centrifugal; Described coking mixed solvent is the mixed solvent of dimethylbenzene and toluene; Described coking mixed solvent and heavy wash oil volume ratio are 1 ︰ 5 ~ 1 ︰ 7; The speed of described gradient cooling is 1 ~ 5 DEG C/h;
B, pre-crystallized solid product is carried out batch distillation, cut fluorenes main distillate fraction;
C, fluorenes main distillate fraction through crystallization, centrifugally obtain Industrial fluorene product.
2. the production technique of Industrial fluorene according to claim 1, is characterized in that: the volume ratio of described dimethylbenzene and toluene is 1:0 ~ 2:1.
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