CN101130479B - Technique for extracting low phenanthrene and anthracene oil from distillation of coal oil and anthracene oil - Google Patents
Technique for extracting low phenanthrene and anthracene oil from distillation of coal oil and anthracene oil Download PDFInfo
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Abstract
The invention discloses an extracting technology of low phenanthrene anthracene oil from coal-tar oil distillate, which comprises the following steps: allocating coal-tar anthracene oil A and high content dimethylbenzene dissolvent B into miscible liquids proportionally in crystallizing container; extracting the low phenanthrene anthracene oil through stockpile crystallization, cold washing, hot washing, melting sequentially. In comparison with the traditional technology, the invention is characterized by the following: lowing content of the phenanthrene to improve the introduction quality; reducing cooling load capacity of the crystallizing container and saving time by using high low tow-phase diaphoresis action; reducing the damage of anthracene and carbazoles; enhancing enriched quantity of the anthracene and the carbazoles; dislodging the phenanthrene in the crystallization by increasing balance time of cold washing and temperature control; dissolving easier through increasing four scouring procedures step by step to dislodge the phenanthrene in the crystallization to high degree and save the total needing time.
Description
Technical field
The present invention relates to extract intermediate from coal tar carbolineum fraction, more specifically refer to a kind of technology of extracting low luxuriant and rich with fragrance carbolineum from coal tar carbolineum fraction, it mainly is to remove phenanthrene, enrichment anthracene, carbazole from coal tar carbolineum fraction.
Background technology
Low luxuriant and rich with fragrance carbolineum be a kind of be raw material with the isolating carbolineum fraction of coal tar distillation, by means such as crystallization dissolvings, obtain with anthracene and carbazole is the mixing oils of main ingredient, its Sino-Philippines content is lower than 1～2%, anthracene content is higher than 10～12%, carbazole content is higher than 3～4%, and this oils can further be produced the low crude anthracene of luxuriant and rich with fragrance content, also can distinguish the anthracene and the carbazole of direct purifying high-purity.As from the foregoing, low luxuriant and rich with fragrance carbolineum is not the composition by the chemosynthesis gained, but adopts extract in the middle of a kind of between the finished product phenanthrene that extracts from the carbolineum fraction, anthracene, the carbazole.
After testing: the main ingredient of the carbolineum fraction that distills out from coal tar is anthracene, carbazole and phenanthrene, its content is respectively 4～8%, 1～4% and 29～45%, these three kinds of components are the important source material and the intermediate product of chemical engineering industry, be widely used in the fields such as dyestuff, agricultural chemicals, leather, plastics, papermaking, and they are along with the reach of science, and its purposes enlarges day by day.In recent years, the exploitation of novel high-energy fuel-perhydro phenanthrene that phenanthrene is developed in aviation field, and produce by carbazole have high antioxidant, the application of the plastics of novel " the N-vinylcarbazole " of good characteristic such as dielectricity and thermostability, cause people to how more effective separation or the concern and the attention of extracting these products.
At present, the extraction crude anthracene or the anthracene of high density, the production method of carbazole have following several, specific as follows in the carbolineum fraction that distills out from coal tar:
(1) direct method: be that raw material directly extracts crude anthracene or the anthracene of direct purifying high-purity and the production route of carbazole promptly from coal tar carbolineum fraction.
A) apply for that with Anshan Iron and Steel Company disclosed CN1161951A and Jiuquan Iron ﹠ Steel Co. apply for that disclosed CN1080276A is representative, what above-mentioned publication number adopted is two-stage crystallization method, directly produce crude anthracene, the quality of gained crude anthracene is 32～35% anthracene, 12～14% carbazole, 10～12% phenanthrene.This method adopts steps such as directly outer spray water coolant, filtration, easily causes environmental pollution.
B) apply for that with Rategers VFT AG disclosed CN1487910A is representative, adopt the fusion-crystallization method to obtain the pure carbazole of pure anthracene; Apply for that with Beijing combustion gas Coal Chemical Industry institute disclosed CN1121103A is representative, adopt the mixed extractant solvent precipitator method directly to produce anthracene, the carbazole of high purity (greater than 90%), there is the high defective of energy consumption that yields poorly in aforesaid method.
(2) indirect method: be that raw material makes intermediate product earlier with coal tar carbolineum fraction promptly---low luxuriant and rich with fragrance carbolineum is the raw material anthracene that removes to produce the finished product crude anthracene or purifying high-purity, luxuriant and rich with fragrance production route with low luxuriant and rich with fragrance carbolineum again.The key that indirect method is produced route is to depend on how to provide a kind of reasonably low luxuriant and rich with fragrance carbolineum production method.
Method with the low luxuriant and rich with fragrance carbolineum of French BEFS company's introduction extraction is representative.This method is to adopt coal tar carbolineum fraction and organic solvent C the flash oil SN of trimethylbenzene 40～50% and dimethylbenzene 8～10% (promptly based on), both are after 62: 38 ratio is made into mixed solution by weight percentage, wash (technology of not establishing temperature control and soaking time), four heat washings (four the unconverted technology of temperature), once fusing through seven windrow crystallizations (technology of step cooling and first sweating), twice cold wash in the crystallizer of sealing, this four big operation is formed original technical process.At last, the whole low luxuriant and rich with fragrance carbolineum that is extracted is molten state, be drained into low luxuriant and rich with fragrance carbolineum made in the finished product storage tank from crystallizer through pipeline, i.e. its component of discharge opeing anthracene content 5～9%, carbazole content 2～3%, luxuriant and rich with fragrance content by weight percentage is 0.5～2%; Its technology total time is 74～82 hours, and carbolineum fraction processing power is 4.4～4.8 tons/hour.Said extracted technology at first adopts from coal tar carbolineum fraction removes the bigger phenanthrene of content, and enrichment anthracene and carbazole, thereby reduced total production energy consumption and cost; Whole process of production is in addition all carried out environmentally safe in the sealing crystallizer of routine and pipeline.Yet former technology also exists total reaction time long, and processing power is lower, and product quality still remains defectives such as raising.For this reason, need us that the technology that adopts indirect method to extract low luxuriant and rich with fragrance carbolineum is further improved.
Summary of the invention
Deficiency for the existence that solves prior art, order of the present invention provides the technology of extracting low luxuriant and rich with fragrance carbolineum from coal tar anthracene fraction that a kind of time is short, yield is high, product are of fine quality, adopt the low luxuriant and rich with fragrance carbolineum of technology gained of the present invention can further produce the lower crude anthracene of its luxuriant and rich with fragrance content, also can be used to continue direct purifying high-purity anthracene and carbazole with less energy consumption and cost.
For achieving the above object, the present invention adopts following technical scheme:
The technology of extracting low luxuriant and rich with fragrance carbolineum from coal tar carbolineum fraction may further comprise the steps,
At first, coal tar carbolineum fraction A and the high-load solvent B of dimethylbenzene are made into mixed solution in proportion and are placed in the crystallisation vessel; Its main ingredient of this solvent B and weight percent are: toluene class content is 1～5%; Xylene content is 70～90%; Trimethylbenzene class content is 0.4～3%; Indane content is 0.1～1%, and indenes content is 0.1～1%; Coal tar carbolineum fraction A and solvent B configuration proportion are 1: 1～2;
Process successively then,
The windrow crystallization, the mode by two step coolings and high and low temperature sweating is carried out crystallization to the mixed solution of coal tar carbolineum fraction A and solvent B; Described windrow crystallization may further comprise the steps: coal tar carbolineum fraction A and solvent B are mixed in proportion are placed in the crystallization raw material tank, do preliminary cooling by the water coolant of its trench bottom heat exchange; Preliminary cooled mixed liquor is entered further crystallisation by cooling processing once more of do in the crystallizer by pipeline, and contain luxuriant and rich with fragrance solvent B after will handling by outside the pipeline discharge crystallizer, the xln that has a small amount of mother liquor is stayed in the crystallizer; Successively carry out low temperature sweating and high temperature sweating again and handle, after sweating finished, its twice sweating discharged outside the crystallizer by pipeline respectively, and its xln is still stayed the windrow crystallization treatment that promptly changes in the crystallizer next time; Above step repeats seven times again, and omits last sweating and handle, will discharge finish after, xln is stayed in the crystallizer, promptly changes afterwards one cold wash over to and washs operation; Described preliminary cool but temperature is 70～80 ℃, cooling temperature is 5～7 ℃ once more, and low temperature sweating treatment temp is 15～30 ℃, and high temperature sweating treatment temp is 30～66 ℃, the height sweating time is 60～120 minutes, and each windrow crystallization time is 4.5～5.5 hours;
Cold wash is washed, and adopts solvent B that xln is carried out cold wash with normal temperature and washs;
The heat washing adopts solvent B to carry out the heat washing to wash xln through cold wash with being lower than 100 ℃; Described heat washing may further comprise the steps: the xln after will washing through cold wash carries out four heat washings again with solvent B, wherein, hot wash temperature is 83～85 ℃ for the first time, hot wash temperature is 85～87 ℃ for the second time, hot for the third time wash temperature is 87～90 ℃, the 4th time hot wash temperature is 90～92 ℃, and each hot carrying out washing treatment time is 4.5～5.5 hours; Then, discharge respectively outside the crystallizer by pipeline containing luxuriant and rich with fragrance solvent B after four hot carrying out washing treatment, its xln is stayed in the crystallizer, changes melting process over to;
Fusing still adopts molten B to the xln melt processed through overheated washing, extracts the low luxuriant and rich with fragrance carbolineum that is molten state.
Described cold wash is washed operation and further be may further comprise the steps:
With solvent B with handle through the windrow Crystallization Procedure after stay xln in the crystallizer
The cold wash that carries out twice is washed processing respectively,
It is 20～30 ℃ that cold wash is washed temperature,
Be incubated 10～20 minutes,
Each carrying out washing treatment time is 1～2 hour;
Then twice cold wash washed and contained luxuriant and rich with fragrance solvent B after the processing and discharge respectively outside the crystallizer by pipeline,
After discharging finished, its xln was stayed in the crystallizer,
Change hot washing procedure over to.
Described fusing is carried out the heat temperature raising fusing to the mixture that is made of xln and solvent B in the crystallizer,
Temperature of fusion is 120 ℃, and fusing time is 4.5～5.5 hours,
Liquid after the fusing is the final low luxuriant and rich with fragrance carbolineum that forms.
In above-mentioned technical scheme of the present invention, compare with traditional technology, owing to adopted and contain the high-load solvent B of dimethylbenzene, solvent B is stronger to the dissolving power of phenanthrene, therefore makes the content of low luxuriant and rich with fragrance carbolineum China and Philippines lower, product quality increases;
Mode by cooling of two steps and high and low temperature sweating, thereby, reduce the cooling load amount of crystallizer and shortened cooling time, simultaneously owing to adopt two sections sweatings of height to handle to have reduced the loss amount of anthracene, carbazole in the sweating, in addition, owing to increased windrow crystalline number of times, improved the enriching quantity of anthracene and carbazole;
Besides, starting time and temperature control, progressively four hot washing procedures of Sheng Gaoing that cold wash is washed have been increased, xln is fully contacted with heat, cold wash liquid, easier dissolving can be removed the intravital phenanthrene of crystallization to a greater extent, has shortened the needed time of total technology.
Description of drawings
Fig. 1 is a process flow diagram of the present invention;
Fig. 2 is the detailed process flow synoptic diagram of embodiment.
Among the figure:
1, carbolineum fraction storage tank; 2, crystallizer; 3, discharge opeing storage tank; 4, sweating storage tank; 5, cold washings storage tank; 6, once heat is washed storage tank; 7, secondary heat washing storage tank; 8, solvent storage tank; 9, crystallization raw material tank; 10, final storage tank; L1～L17 is pipeline.
Embodiment
The technology that in " summary of the invention ", discloses according to the present invention, below the equipment of this technology and use describe its technological process again in detail:
At first, see also Fig. 1, raw material-coal tar carbolineum fraction A and the high-load solvent B of dimethylbenzene are made into mixed solution by a certain percentage in the crystallisation vessel of sealing, wash, four heat washings, and the four big operations that once melt through eight windrow crystallizations, twice cold wash.The last whole low luxuriant and rich with fragrance carbolineum that is extracted is molten state, passes through pipeline from crystallizer and is drained in the finished product storage tank, and made low luxuriant and rich with fragrance carbolineum is discharge opeing, and it forms by weight percentage that anthracene content is 13～27%; Carbazole content is 4～8%; Luxuriant and rich with fragrance content is 0.3～1%; Extraction process total time is 60.5～75.5 hours; Carbolineum fraction processing power is 5.0～5.2 tons/hour.
Above-mentioned solvent B is the dedicated solvent that number of patent application CN200510028923.9 is disclosed, and its main ingredient of this solvent B and weight percent are: toluene class content is 1～5%; Xylene content is 70～90%; Trimethylbenzene class content is 0.4～3%; Indane content is 0.1～1%, and indenes content is 0.1～1%.
Its both configuration proportions of coal tar carbolineum fraction A and solvent B are 1: 1～2.
Eight windrow crystallizations are to be mixed in proportion in the crystallization raw material tank by coal tar carbolineum fraction A and solvent B to do preliminary cooling by the water coolant of its trench bottom heat exchange earlier, enter by pipeline again and do further crystallisation by cooling processing in the crystallizer, thereafter the solvent B that contains phenanthrene etc. is by outside the pipeline drain tank, its xln that has a small amount of mother liquor is stayed in the crystallizer, row successively carries out low temperature sweating and high temperature sweating processing again, after sweating finishes, its twice sweating promptly contains luxuriant and rich with fragrance solvent B respectively by outside the pipeline drain tank, its xln is still stayed the windrow crystallization treatment that promptly changes in the crystallizer next time, above step repeats seven times again, last omission sweating is handled, discharging finishes the post crystallization body stays in the crystallizer, promptly changes cold wash over to and washs operation.Processing parameter is as follows: preliminary cool but temperature is 70～80 ℃, final cooling temperature is 5～7 ℃, and the low temperature sweating temperature is 15～30 ℃, and the high temperature sweating temperature is 30～66 ℃, twice sweating total time is 60～120 minutes, and each windrow crystallization time is 4.5～5.5 hours.
It is to carry out the twice pair of xln of staying in the crystallizer respectively and carry out twice totally cold wash and wash processing by washed solvent B stored in the storage tank by cold wash that twice cold wash washed, its purpose continues dissolving crystallized intravital phenanthrene by secondary washing, its the twice cold washings in processing back promptly contains luxuriant and rich with fragrance solvent B and enters discharge opeing storage tank and crystallization raw material tank respectively by pipeline, after discharging finishes, its xln is stayed in the crystallizer, changes next step hot washing procedure over to.The processing parameter that cold wash is washed is: it is 20～30 ℃ that cold wash is washed temperature, is incubated 10～20 minutes, and each carrying out washing treatment time is 1～2 hour.
Four heat washings are adopted respectively by hot rinse bath once, the hot rinse bath of secondary, and the stored solvent B of solvent storage tank three-flute, successively the xln of staying in the crystallizer is carried out hot carrying out washing treatment four times, increase along with the number of times of heat washing, the temperature of each heat washing also progressively raises, and makes it that luxuriant and rich with fragrance content gradually reduces in the xln, and anthracene, the progressively enrichment of carbazole content.Its four hot washingss promptly contain luxuriant and rich with fragrance solvent B by pipeline enter cold washings storage tank respectively, once in the groove of hot washings storage tank and the hot washings storage tank of secondary, after discharging finished, its xln was stayed in the crystallizer, changes over to once to melt operation.The processing parameter of heat washing is: hot wash temperature is 82～85 ℃ for the first time, hot wash temperature is 85～87 ℃ for the second time, hot for the third time wash temperature is 87～90 ℃, and the 4th time hot wash temperature is 90～92 ℃, and each hot carrying out washing treatment time is 4.5～5.5 hours.
Fusing is to adopt to be entered in the crystallizer by solvent B stored in the solvent storage tank, through heat temperature raising, make xln begin to dissolve, when reaching temperature of fusion, its xln is discharged crystallizer with molten state, enters at last in the finished product storage tank by pipeline again, and its discharge opeing is made low luxuriant and rich with fragrance carbolineum, fusing time is 4.5～5.5 hours, and temperature of fusion is 120 ℃.
Need to prove that discharge opeing that employed solvent B in each above-mentioned operation and each operation are handled circulates uses repeatedly, and entire reaction course is to carry out in airtight container and pipeline.
Compare with traditional technology, technology of the present invention has following tangible advantage:
1) to have adopted solvent be to contain dimethylbenzene up to 70～90% solvent B in the present invention, much better than to the solvency power of phenanthrene because dimethylbenzene contains dimethylbenzene less (8～10%) to the dissolving power of phenanthrene is strong with original solvent orange 2 A, causes the content of low luxuriant and rich with fragrance carbolineum China and Philippines lower.
2) the present invention adopts has increased a windrow crystallization than traditional technology, has improved the enriching quantity of anthracene and carbazole.And to the bigger change of each windrow crystalline processing condition do, be embodied in: 1. former once cooling before this, now change into by the heat exchanger tube of crystallization raw material tank bottom land and do preliminary cooling earlier, enter again and further continue to be cooled to 5～7 ℃ in the crystallizer, thereby, reduce crystalline cooling load amount and shortened cooling total time.2. adopt two sections sweatings of height to handle to reduce the loss amount of anthracene, carbazole in the sweating, improved luxuriant and rich with fragrance removal amount, its anthracene is 13～27% in the obtained low luxuriant and rich with fragrance carbolineum.Carbazole is 4～8% all to improve 2～3 times than traditional technology.
3) the present invention adopts the increase cold wash to wash and handles starting time and temperature control; Also adopt by four hot washing procedures of elevated temperature progressively, xln is fully contacted with the hot and cold washings that solvent B forms, easier dissolving, thereby, can remove the intravital phenanthrene of crystallization to greatest extent, the Sino-Philippines content of products obtained therefrom is than traditional technology low 50%.
4) the present invention enters different storage tank internal recycle respectively and uses by the different various treatment solutions of luxuriant and rich with fragrance content, thereby reduces the usage quantity of solvent, reduces total cost.
5) the whole extraction process of the present invention all reaches in the crystallisation vessel of sealing and the pipeline and carries out, environmentally safe, and its production cycle has shortened 6.5～14 hours than original technology, and its art breading ability has improved 0.4～6 ton/hour.
Be raw material with the carbolineum fraction A of luxuriant and rich with fragrance 29～45%, anthracene content 4～8%, carbazole content 1～4% more below,, specifically describe as follows technical process according to Fig. 2:
1. eight windrow crystallizations
Solvent B enters crystallization raw material tank 9 by solvent storage tank 8 by pipeline L1, the carbolineum fraction enters crystallization raw material tank 9 by carbolineum fraction storage tank 1 by pipeline L2, both are according to after 1: 1 mixed, anthracene content is 6.07% in the composition, and carbazole content is 2.05%, and luxuriant and rich with fragrance content is 19.93%, pass through the water coolant of storage tank bottom heat exchanger tube earlier, make temperature be cooled to 75 ℃, mixed solution has reduced the cooling load of crystallizer after preliminary cooling, shortened cooling time.Enter in the crystallizer 2 by pipeline L3 again, through recirculated water and progressively cooling of refrigerated water cooling, further cool off once more until 7 ℃, cooling stops, the solvent B that crystallizer 2 contains molten Jie's thing such as phenanthrene by pipeline L4 to sump pit 3 discharge opeings, the xln that contains a small amount of mother liquor after discharge opeing finishes is stayed in the crystallizer 2, crystallizer 2 is warming up to 20 ℃ of low temperature sweatings then, its sweating is delivered to discharge opeing liquid bath 3 by pipeline L5, when crystallizer 2 temperature rise to 66 ℃ by 30 ℃, the high temperature sweating stops, in its device 2 the high temperature sweating deliver to sweating liquid bath 4 by pipeline L6, the high low temperature sweating time is 90 minutes.Each windrow crystallization treatment time is 4.5 hours.
Above step repeats seven times again, cancels sweating for the last time, i.e. discharging finishes post crystallization stays in the crystallizer 2, changes cold wash over to and washs operation.
2. twice cold wash washed
For the first time cold washings is by the stored solvent B of cold washings storage tank 5, enter in the crystallizer 2 by pipeline L7, having advanced cold washings is that temperature is under 30 ℃ of conditions, after the balance 15 minutes, to 3 discharge opeings of discharge opeing storage tank, anthracene content was 1.92% during discharge opeing was formed by pipeline L8, and carbazole content is 0.63%, luxuriant and rich with fragrance content is 14.46%, and its xln is stayed in the crystallizer 2.Change for the second time cold wash over to and wash processing, 1.5 hours consuming time of whole process.
For the second time cold washings is by the stored solvent B of cold washings storage tank 5, enter crystallizer 2 by pipeline L7, having advanced cold washings is balance after 15 minutes under 30 ℃ of conditions in wash temperature, by pipeline L9 to 9 discharge opeings of crystallization raw material tank, anthracene content was 1.68% during discharge opeing was formed, and carbazole content is 0.5%, and luxuriant and rich with fragrance content is 8%, its xln is stayed in the crystallizer 2, will change the washing of subsequent processing heat over to.1.5 hours consuming time of whole process.
Wash starting time by increasing cold wash, crystal is fully contacted with cold washings in crystallizer, remove the phenanthrene in the crystal to greatest extent; Owing to get the Sino-Philippines content difference of cold washings twice, drain into discharge opeing storage tank 3 and crystallization raw material tank 9 respectively after therefore twice cold wash being washed.
3. four heat washings
Heat washing for the first time is by stored solvent B in the heat washing storage tank 6 once, enter the crystallizer 2 that has heated up by pipeline L10, its xln begins fusing, 2 temperature reaches 83 ℃ in crystallizer, utilizes balance to make material concentration full and uniform, changes into cooling again, cooling begins by pipeline L11 to cold washings storage tank 5 discharge opeings after finishing, anthracene content was 2.76% during discharge opeing was formed, and carbazole content is 0.77%, and luxuriant and rich with fragrance content is 7.37%.After discharge opeing finished, crystallizer 2 intercrystalline bodies changed heat washing for the second time over to.5 hours consuming time of whole process.
Heat washing for the second time is by the solvent B that stores in the secondary heat washing storage tank 7, enter the crystallizer 2 that has heated up by pipeline L12, its xln begins fusing, 2 temperature reaches 85 ℃ in crystallizer, utilizes balance to make material concentration full and uniform, and then changes into and cooling, cooling begins by pipeline L13 to cold washings storage tank 5 discharge opeings after finishing, anthracene content was 2.35% during discharge opeing was formed, and carbazole content is 0.66%, and luxuriant and rich with fragrance content is 3.72%.After discharge opeing finished, crystallizer 2 intercrystalline bodies changed heat washing for the third time, 5 hours consuming time of whole process over to.
Heat washing for the third time is by the stored solvent B of solvent storage tank 8, enter the crystallizer 2 that has heated up by pipeline L14, its xln begins fusing, 2 temperature reaches 87 ℃ in crystallizer, and the portion balance of utilization makes material concentration full and uniform, and then changes into and cooling, after finishing, cooling begins by pipeline L15 to once heat washing storage tank 6 discharge opeings, anthracene content was 1.9% during discharge opeing was formed, and carbazole content is 0.48%, and luxuriant and rich with fragrance content is 1.72%.After discharge opeing finished, crystallization was stayed and is changed the 4th heat washing, 5 hours consuming time of whole process in the crystallizer 2 over to.
The 4th heat washing is by the solvent B that stores in the solvent storage tank 8, enter the crystallizer 2 that has heated up by pipeline L14, its xln of when filling with substance begins fusing, continues heat fused after charging is finished, up to 90 ℃ of crystallizer 2 Nei Wenduda, utilize balance to make material concentration full and uniform, change into then and cooling, cooling finish the back by pipeline L16 to 7 discharge opeings of secondary heat washing storage tank, anthracene content was 2.07% during discharge opeing was formed, carbazole content is 0.54%, and luxuriant and rich with fragrance content is 0.91%.After discharge opeing finished, crystallizer 2 intercrystalline bodies changed the thawing operation over to.5 hours consuming time of whole process.
Along with the increase of hot washing times, the luxuriant and rich with fragrance content in the xln can gradually reduce, and anthracene, the progressively enrichment of click content also progressively raise with the hot wash temperature of the increase of number of times in addition, thereby helps the enrichment of anthracene, click and remove luxuriant and rich with fragrance.
4. fusing
Solvent B with solvent storage tank 8 stores enters the crystallizer 2 that has heated up by pipeline L14, begins fusing then.When temperature of fusion reaches 120 ℃, utilize balance to make material concentration full and uniform, at last with the low luxuriant and rich with fragrance carbolineum of whole fusions in the crystallizer 2, enter the finished product storage tank 10 by pipeline L17, discharge opeing is that anthracene content was 16.26% during made low luxuriant and rich with fragrance carbolineum was formed, carbazole content is 4.64%, and luxuriant and rich with fragrance content is 0.43%.5 hours consuming time of whole process.
Present embodiment purifying technique total time is 68 hours, and carbolineum fraction processing power is 5.2 tons/hour.
With above-mentioned luxuriant and rich with fragrance content 29～45% (wt%), anthracene content 4～8% (wt%), the carbolineum fraction A of carbazole content 1～4% (wt%), produce low luxuriant and rich with fragrance carbolineum according to technology of the present invention and traditional technology and carry out following comparison:
As can be seen from the above table, the low luxuriant and rich with fragrance carbolineum quality that the present invention produces is better than the product that traditional technology is produced, and production efficiency and ability also improve greatly.
Claims (3)
1. from coal tar carbolineum fraction, extract the technology of low luxuriant and rich with fragrance carbolineum,
It is characterized in that,
This method comprises the steps:
At first, coal tar carbolineum fraction A and the high-load solvent B of dimethylbenzene are made into mixed solution in proportion and are placed in the crystallisation vessel; In solvent B, toluene level is 1～5%; Xylene content is 70～90%; Trimethylbenzene content is 0.4～3%; Indane content is 0.1～1%, and indenes content is 0.1～1%; Coal tar carbolineum fraction A and solvent B configuration proportion are 1: 1～2;
Process successively then,
The windrow crystallization, the mode by two step coolings and high and low temperature sweating is carried out crystallization to the mixed solution of coal tar carbolineum fraction A and solvent B; Described windrow crystallization may further comprise the steps: coal tar carbolineum fraction A and solvent B are mixed in proportion are placed in the crystallization raw material tank, do preliminary cooling by the water coolant of its trench bottom heat exchange; Preliminary cooled mixed liquor is entered further crystallisation by cooling processing once more of do in the crystallizer by pipeline, and contain luxuriant and rich with fragrance solvent B after will handling by outside the pipeline discharge crystallizer, the xln that has a small amount of mother liquor is stayed in the crystallizer; Successively carry out low temperature sweating and high temperature sweating again and handle, after sweating finished, its twice sweating discharged outside the crystallizer by pipeline respectively, and its xln is still stayed the windrow crystallization treatment that promptly changes in the crystallizer next time; Above step repeats seven times again, and omits last sweating and handle, and after discharging finished, xln was stayed in the crystallizer, promptly changes one cold wash in back over to and washs operation; Described preliminary cool but temperature is 70～80 ℃, cooling temperature is 5～7 ℃ once more, and low temperature sweating treatment temp is 15～30 ℃, and high temperature sweating treatment temp is 30～66 ℃, the height sweating time is 60～120 minutes, and each windrow crystallization time is 4.5～5.5 hours;
Cold wash is washed, and adopts solvent B that xln is carried out cold wash with normal temperature and washs;
The heat washing, may further comprise the steps: the xln after will washing through cold wash carries out four heat washings again with solvent B, wherein, hot wash temperature is 83～85 ℃ for the first time, hot wash temperature is 85～87 ℃ for the second time, hot for the third time wash temperature is 87～90 ℃, and the 4th time hot wash temperature is 90～92 ℃, and each hot carrying out washing treatment time is 4.5～5.5 hours; Then, discharge respectively outside the crystallizer by pipeline containing luxuriant and rich with fragrance solvent B after four hot carrying out washing treatment, its xln is stayed in the crystallizer, changes melting process over to;
Fusing still adopts solvent B to the melt processed of heating through the xln of overheated washing, extracts the low luxuriant and rich with fragrance carbolineum that is molten state.
2. the technology of the low luxuriant and rich with fragrance carbolineum of extraction as claimed in claim 1,
It is characterized in that,
Described cold wash is washed operation and further be may further comprise the steps:
With solvent B with handle through the windrow Crystallization Procedure after the cold wash that xln in the crystallizer carries out twice respectively of staying wash processing, it is 20～30 ℃ that cold wash is washed temperature, be incubated 10～20 minutes, the carrying out washing treatment time is 1～2 hour at every turn; Then twice cold wash washed and contained luxuriant and rich with fragrance solvent B after the processing and discharge respectively outside the crystallizer by pipeline, after discharging finished, its xln was stayed in the crystallizer, changes hot washing procedure over to.
3. the technology of the low luxuriant and rich with fragrance carbolineum of extraction as claimed in claim 1,
It is characterized in that:
Described fusing is carried out the heat temperature raising fusing to the mixture that is made of xln and solvent B in the crystallizer, and temperature of fusion is 120 ℃, and fusing time is 4.5～5.5 hours, and the liquid after the fusing is the final low luxuriant and rich with fragrance carbolineum that forms.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2006100303635A CN101130479B (en) | 2006-08-24 | 2006-08-24 | Technique for extracting low phenanthrene and anthracene oil from distillation of coal oil and anthracene oil |
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| CN2006100303635A CN101130479B (en) | 2006-08-24 | 2006-08-24 | Technique for extracting low phenanthrene and anthracene oil from distillation of coal oil and anthracene oil |
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| US3505361A (en) * | 1964-01-27 | 1970-04-07 | Koppers Co Inc | Preparation of anthraquinone from crude coal tar |
| DE2020973A1 (en) * | 1970-04-29 | 1971-11-18 | Ruetgerswerke Ag | Process for obtaining pure anthracene from the anthracenoel of Sn coal tar |
| DE3040431A1 (en) * | 1979-10-25 | 1981-05-07 | Instytut Chemii Przemysłowej, Warszawa | METHOD FOR DETERMINING AND PURIFYING ANTHRACEN FROM ANTHRACENOIL |
| CN1487910A (en) * | 2001-01-24 | 2004-04-07 | ���ظ�˹��ѧ�����ɷ�����˾ | Obtaining anthracene and carbazole by melt-crystallization |
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| US3505361A (en) * | 1964-01-27 | 1970-04-07 | Koppers Co Inc | Preparation of anthraquinone from crude coal tar |
| DE2020973A1 (en) * | 1970-04-29 | 1971-11-18 | Ruetgerswerke Ag | Process for obtaining pure anthracene from the anthracenoel of Sn coal tar |
| DE3040431A1 (en) * | 1979-10-25 | 1981-05-07 | Instytut Chemii Przemysłowej, Warszawa | METHOD FOR DETERMINING AND PURIFYING ANTHRACEN FROM ANTHRACENOIL |
| CN1487910A (en) * | 2001-01-24 | 2004-04-07 | ���ظ�˹��ѧ�����ɷ�����˾ | Obtaining anthracene and carbazole by melt-crystallization |
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