CN1025183C - Method for isolation and purification of coal tar-derived anthracene - Google Patents
Method for isolation and purification of coal tar-derived anthracene Download PDFInfo
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- CN1025183C CN1025183C CN89108882A CN89108882A CN1025183C CN 1025183 C CN1025183 C CN 1025183C CN 89108882 A CN89108882 A CN 89108882A CN 89108882 A CN89108882 A CN 89108882A CN 1025183 C CN1025183 C CN 1025183C
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- Prior art keywords
- anthracene
- crystallizer
- carbolineum
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000011280 coal tar Substances 0.000 title claims description 7
- 238000000746 purification Methods 0.000 title claims description 3
- 238000002955 isolation Methods 0.000 title description 2
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 230000005484 gravity Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000002425 crystallisation Methods 0.000 claims description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 238000000956 solid--liquid extraction Methods 0.000 claims 1
- 238000007865 diluting Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000001172 liquid--solid extraction Methods 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 15
- 239000003921 oil Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/20—Polycyclic condensed hydrocarbons
- C07C15/27—Polycyclic condensed hydrocarbons containing three rings
- C07C15/28—Anthracenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/14—Purification; Separation; Use of additives by crystallisation; Purification or separation of the crystals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for separating purified anthracene from a coalite oil raw material through the methods of crystallizing and liquid-solid extraction. The present invention is characterized in that the anthracene oil existing in a diluting type possibly is cooled in a vertical crystallizer with the cooling surface temperature being lower than 80 degree, the residual oil is separated under the gravity action, the crude anthracene crystal formed in the same crystallizer is processed with an aprotic amphiphatic solvent, then the purified anthracene is separated from the suspending liquid with the filtrating, centrifuging and other known methods, and the recovered solvent can be reused in the process.
Description
Involved in the present invention is a kind of the separation from coal tar raw material and the method for purifying anthracene.
The method of separation and purifying anthracene long ago just is out of use from the coal tar fraction that the chemical conversion thing or its important impurity of anthracene are formed, in present industrial production, only use people such as J.polaczek at " przemysl Chemiczny " 60,168-170(1981) distillation described in and crystallization process.
Chemical industry is mainly interested in the isolating crystallization process of anthracene, and this is because compare with distillation method, the cause that its power consumption is low.And distillation method is owing to the high freezing point of anthracene and carbazole that produces and phenanthrene is brought extra operational difficulty thereupon.
In typical commercial run, carbolineum can be by being cooled to 30-70 ℃ and crystallization, and is then, centrifugal or filter crude anthracene xln and single or multiple from solvent such as pyridine bases, recrystallization in acetone or the toluene, final step are to isolate the purifying anthracene through centrifugal or filtration from mother liquor.This method has many shortcomings relevant with many compositional characteristics of carbolineum and crude anthracene, thereby causes the low selectivity of crystallization process and make the separation of xln in the discharging oil become difficult.In rotary crystallizer, make in the carbolineum crude anthracene crystalline result form many tiny crystallizations, and a large amount of oil contaminants are arranged at these xln surface adsorptions.Therefore, the relative efficiency of isolating crude anthracene from carbolineum is lower, and the loss of anthracene is very big in the Residual oil.In addition, the recrystallization of crude anthracene also can cause the loss of sizable energy consumption and solvent for use in typical solvent.
The improvement (as disclosing in patent documentation) of the crystallization process of anthracene separation and purifying helps some improvement of these method economic conditions, but does not cause any improvement in essence.
In polish patent application numbers 131628 and 131664, disclosed the method in two stages of a kind of application that comprises the carbolineum thinner and this technology, but, the quality and the output that increase crude anthracene are no any improvement in essence under crystal nucleation and growth conditions, or do not have under the remarkable increase state at the partial regression coefficient of anthracene between crystallization phases and mother liquor, obtain by the input of optional equipment (mixing tank and whizzer).
In addition, as in the past, always need be with a kind of solid work in-process isolated in form anthracene.But, and make operation become difficult especially because the inevitable content of some oily matters has hindered a kind of gas transhipment fragility essential and product of exact dosage desired in being further purified process.
The application of new selective solvent as describing, has improved its efficient to a great extent in the process of anthracene purifying in polish patent application numbers 137241.But new device is set up in the enforcement that the application of crude anthracene sepn process is required to be these processes.
The inventive method is better than separating the method with the purifying coal tar-derived anthracene.
In the methods of the invention, carbolineum is incorporated in the vertical crystallizer that has more perfect heat exchange surface, preferably being incorporated into a kind of heat-eliminating medium can be in pipe in the mobile tubular crystallizer of space, in this crystallizer, be cooled to them below 80 ℃ then, preferably be cooled to 0～70 ℃, and keep this temperature and reach 2～20 hours, be preferably in discharging mother liquor under the action of gravity, formed crude anthracene xln in same crystallizer with a kind of non-proton dipolar nature solvent treatment, the ideal quantity of solvent is a 40-250%(weight), and temperature range is 20～60 ℃, the last purifying anthracene that exists with the solid phase that is suspended in the solvent after filtration, centrifugal or other currently known methods separates, washing is also dry, and solvent is renewable and recycle.
Just in case just carbolineum contains solid pollutant, when particularly quinoline non-soluble α-2 composition of coal tar derived existed, desirable method was with its preliminary filtration, preferably uses filtration adjuvant, as the breeze filter bed, or use a kind of slit strainer that can outside remove separate piece.
Another kind of desirable method is to repeat several times the refrigerative of initial carbolineum part to be operated in crystallizer, particularly at first carbolineum anthracene content lower (being lower than 5%), at least account for crystallizer volumetrical one half to crude anthracene xln volume, because might utilize the throughput of equipment so better.
Another desirable method is to utilize the suitable dilution agent to dilute carbolineum just, and whether freezing fully this can make the crude anthracene crystallisation procedure does carry out under need not to worry the low-temperature condition of composition in the crystallizer.As for thinner, preferably select the aliphatics or the alicyclic C of straight chain and side chain for use
5-C
12-hydro carbons, or the hydro carbons in the formula I (wherein R is C
2-C
3-alkyl, n are an integer among the 1-5) and twice or the isopropyl derivative of the naphthalene that repeatedly replaces or their mixture, its amount accounts for 20～100%(weight of used carbolineum).The best way is to use such as the dialkyl benzene and the polyalkylbenzene cut that obtain from benzene and ethene or propylene alkylation process aliphatic gasoline and cracked oil, or the technical products of propylene oligomer one class.Because these thinner costs are low, so needn't reclaim and regenerate, they can remain in the carbolineum of discharging, and they can be used in the manufacturing of carbon black as coal carboline or a kind of undressed material.
As non-proton dipolar nature solvent (being used to handle crude anthracene crystallization), preferably select organic amide, alum or nitrile for use, particularly the acid amides in the general formula II, wherein R attached on the crystallizer wall
1Be hydrogen atom or C
1-C
3-alkyl, R
2Be hydrogen atom, methyl or ethyl, R
3Be C
1-C
3-alkyl, or R
2And R
3Be C together
3-C
6-alkylidene group, and R
1And R
3Be C together
2-C
7Alkylidene group, oxa-alkylidene group or azepine alkylidene group.The non-proton dipolar nature solvent of this class comprises a following kind solvent, as N-Methyl pyrrolidone, and N-methyl-hexanolactam, N,N-dimethylacetamide, the N-methylformamide, the mixture of N-N-formyl morpholine N-or they and water, and dimethyl sulfoxide (DMSO), acetonitrile and beta-hydroxy propionitrile.
Transfer in the separating device through gravity, strength effect or by a kind of suitable pump with formed crystalloid suspension behind the non-proton dipolar nature solvent treatment crude anthracene, extracting solution separates the resulting pure anthracene crystallization in back earlier with the non-proton dipolar nature solvent that uses in the treating processes, then with a kind of low polar solvent that boils, methyl alcohol particularly, ethanol, water or their mixture, and the mixture of water and acetone and methylethylketone carries out the one or many washing, in last operation steps, with a kind of known operation method drying crystalline body and be processed into anthraquinone or wrap up with cloth bag.The further processing of isolated extracting solution also might be isolated carbazole with applied non-proton dipolar nature solvent in the recycling process.The method of carrying out solvent reclamation is preferably by vacuum distilling, and water periodically dilutes the diluent of (being preferably 1: 1)) to remove hydro carbons, at last after filtration, centrifugal or other currently known methods, the solid of precipitation separation.
The separation of anthracene of the present invention and purge process and have at pipe internal surface under the cooling conditions of water or saline flow and carry out preferably in a branch of internal diameter is the tubular crystallizer formed of 5～20 millimeters metal tubes.
The present invention is for providing possibility from anthracene content even for producing its purity 3% the carbolineum for the pure anthracene more than 95%, and its total efficiency can reach the 75-80% of every part of anthracene in the raw material.
The following example will be used for method of the present invention is described, but not limit its use range.
Embodiment 1
The carbolineum sample that 214 grams are had listed composition of table 1 and a characteristic is placed in the vertical tube type crystallizer that has a heating jacket.The heating of carbolineum circulating hot water in the crystallizer heating jacket reaches uniform liquid phase (its temperature is above 90 ℃).Then, reduce the circulating water temperature in the heating jacket with 0.1 ℃/minute mean rate and begin slowly cooling oil.This process lasts till that the crystallized temperature of last oil reaches 50 ℃.Composition remained on 50 ℃ of levels lasting 1 hour in the crystallizer.Afterwards, 128 gram mother liquors are through separation by gravity.86 residual gram crude anthracene crystallisation adsorption are on the crystallizer inwall, under same crystallizer room temperature condition, handle them with 120 gram N-Methyl pyrrolidone, after three hours, composition filters through a Buchner funnel with form of suspension in the crystallizer, collects the filtrate that a pure anthracene and 199 grams contain N-Methyl pyrrolidone.The anthracene piece is with two parts of methyl alcohol, every part of 120 milliliters of washings.Can obtain 7 gram purity at last and be 96.8% anthracene (calculate with every part of anthracene, its productive rate be theoretical value 52.8%), vacuum distilling filtrate reclaims 119 gram N-Methyl pyrrolidone and recycle again.
The composition of used carbolineum in the described test of table 1 embodiment 1-5
Component content (, measuring) through the ultraviolet method in weight %
Anthracene 6.0
Luxuriant and rich with fragrance 34.6
Carbazole 1.5
Embodiment 2
The carbolineum sample that 214 grams is had listed composition of table 1 and characteristic is placed in the embodiment 1 described crystallizer.Carbolineum heats by crystallizer heating jacket internal recycle hot water and becomes an even liquid phase (its temperature is above 90 ℃).The same with embodiment 1, cooling oil is upright to reaching 50 ℃ of last crystallized temperatures.Composition continues 1 hour 50 ℃ of levels in the crystallizer, 136 gram mother liquors separate under action of gravity then, residual 78 gram crude anthracene crystallisation adsorption under same crystallizer room temperature condition, are handled them with the 120 gram N-Methyl pyrrolidone that contain 12 gram water (account for weight 10%) on the crystallizer inwall.After three hours, content filters through Buchner funnel with the form of suspension in the crystallizer, collects the filtrate that a pure anthracene and 199 grams contain N-Methyl pyrrolidone.The anthracene piece is through two parts of methyl alcohol, every part of 120 milliliters of washings.Obtain at last 11 the gram purity be that 97.9%(calculates with every part of anthracene, its productive rate be theoretical value 83.9%) anthracene.Vacuum distilling filtrate is also reclaimed 119 gram N-Methyl pyrrolidone.
Embodiment 3
The carbolineum sample that 216 grams is had listed composition of table 1 and characteristic is positioned in the crystallizer as embodiment 1.Carbolineum obtains an even liquid phase (its temperature is above 90 ℃) with the heating of crystallizer heating jacket internal recycle hot water.Then, press the step of embodiment 1, but with 0.2 ℃/minute mean rate, cooling oil is upright to maintaining 60 ℃ of last crystallized temperatures gradually.Content kept one hour 60 ℃ of levels in the crystallizer, and 116 gram mother liquors (Residual oil) rely on separation by gravity afterwards.There are 100 gram crude anthracene crystallizations still to be adsorbed on the crystallizer inwall.Under same crystallizer room temperature condition, handle them with 120 gram N-Methyl pyrrolidone.After three hours, content filters through Buchner funnel with the suspension state in the crystallizer, collects a pure anthracene and 214 grams contain N-Methyl pyrrolidone filtrate.The anthracene piece is through two parts of pure methyl alcohol, every part of 120 milliliters of washings.Obtain at last 6 the gram purity be 95.5%(in every part of anthracene, its productive rate be theoretical yield 44.2%) anthracene.Vacuum distilling filtrate, and reclaim 119 gram N-Methyl pyrrolidone.
Embodiment 4
The carbolineum sample that 220 grams are had listed composition of table 1 and a characteristic is positioned in the crystallizer identical with embodiment 1.Carbolineum is rendered as a kind of even liquid phase (its temperature is above 90 ℃) under the heating of crystallizer heating jacket circulating hot water.Then, as embodiment 1, cooling oil is upright to maintaining 40 ℃ of last crystallized temperatures gradually.Content kept one hour at 40 ℃ in the crystallizer, made 143 gram mother liquors according to separation by gravity afterwards.Still have 77 gram crude anthracenes to be adsorbed on the perisporium in the crystallizer.Handle under same crystallizer room temperature condition with 120 gram N-Methyl pyrrolidone.After three hours,, collect a pure anthracene and 189 grams contain N-Methyl pyrrolidone filtrate with the content that exists with the suspension state in the Buchner funnel filtering for crystallizing device.With two parts of pure methyl alcohol, 120 milliliters every part washing anthracene pieces.Obtain at last 8 the gram purity be 97.8%(in every part of anthracene, its productive rate be theoretical value 59.3%) anthracene.Vacuum distilling filtrate, and reclaim 119 gram N-Methyl pyrrolidone.
Embodiment 5
The crystallization the first step
217 grams are had shown in the table 1 form and the carbolineum sample of characteristic places the same crystallizer of embodiment 1.Utilize the interior circulating hot water heating of crystallizer heating jacket to make carbolineum be and be a kind of uniform liquid phase (its temperature is above 90 ℃).Then, with embodiment 1, cooling until 70 ℃ of last crystallized temperatures gradually.Keep in the crystallizer content 70 ℃ of levels one hour, make 167 gram mother liquors afterwards according to separation by gravity.Still have 50 gram crude anthracene crystallisation adsorption in the crystallizer on perisporium.Handle under same crystallizer room temperature condition with 60 gram N-Methyl pyrrolidone.After three hours, content filters through Buchner funnel with the suspension state in the crystallizer, collects the filtrate that a pure anthracene and 106 grams contain N-Methyl pyrrolidone.The anthracene piece is with two parts of methyl alcohol, every part of 120 milliliters of washings.Obtaining 4 gram purity at last is 95.9% anthracene.With this filtrate and the filtrate merging of crystallization for the second time,, reclaim used solvent together through vacuum distilling.
Second step of crystallization
The 167 gram mother liquors of placing the crystallization first time are to the above-mentioned vertical tubular crystallizer of mentioning.Content in the crystallizer is heated to 70 ℃ is even liquid phase.Afterwards, with embodiment 1, cooling until maintaining 30 ℃ of crystallization final temps gradually.Keep in the crystallizer content 30 ℃ of levels one hour, then, according to separation by gravity 100 gram Residual oils.In the crystallizer, still have 67 gram crude anthracene crystallisation adsorption on perisporium, under same crystallizer room temperature condition, handle with 60 gram N-Methyl pyrrolidone.After three hours, content filters through Buchner funnel with form of suspension in the crystallizer, collects the filtrate that a pure anthracene and 124 grams contain N-Methyl pyrrolidone.The anthracene piece is through two parts of pure methyl alcohol, every part of 120 milliliters of washings.Obtaining 3 gram purity at last is 95.1% anthracene.With filtrate and the filtrate merging and the vacuum distilling of crystallization for the first time, reclaim used solvent.Obtain 119 gram N-Methyl pyrrolidone.Through two-step crystallization, obtaining 7 gram purity is 95.5% anthracene, and in every part of anthracene, corresponding cumulative yield is 51.3%.
Embodiment 6
218 grams are had shown in the table 2 form and the carbolineum sample of characteristic is positioned over in the identical crystallizer of embodiment 1.Carbolineum is through the heating of crystallizer heating jacket circulating hot water and present an even liquid phase (its temperature is above 90 ℃) then, as embodiment 1, and cooling until maintaining 50 ℃ of last crystallized temperatures gradually.Content remained on 50 ℃ of levels one hour in the crystallizer, made 136 gram mother liquors according to separation by gravity afterwards.In the crystallizer, still have 82 gram crude anthracene crystallisation adsorption on perisporium.Handle under same crystallizer room temperature condition with 120 gram N-Methyl pyrrolidone.After three hours, content filters through Buchner funnel with form of suspension in the crystallizer, collects the filtrate that a pure anthracene and 189 grams contain N-Methyl pyrrolidone.The anthracene piece is with three parts of pure methyl alcohol, every part of 120 milliliters of washings.Obtain at last 13 the gram purity be 95.0%(in every part of anthracene, its productive rate be theoretical value 60.9%) anthracene.Vacuum distilling filtrate is recovered to 119 gram N-Methyl pyrrolidone.
The composition of carbolineum in table 2 embodiment 6, the 7 described tests
Component content (, measuring) by ultraviolet in weight %
Anthracene 9.3
Luxuriant and rich with fragrance 40.9
Carbazole 3.8
Embodiment 7
219 grams are had shown in the table 2 form and the carbolineum sample of characteristic is placed in the crystallizer as embodiment 1.Carbolineum is an even liquid phase (its temperature is above 90 ℃) under the heating of crystallizer heating jacket circulating hot water.Then, as embodiment 1, cooling until maintaining 70 ℃ of last crystallized temperatures gradually.Content kept one hour 70 ℃ of levels in the crystallizer, made 148 gram mother liquors according to separation by gravity afterwards.In the crystallizer, still have 71 gram crude anthracene xln to be adsorbed on the perisporium.Handle under same crystallizer room temperature condition with 120 gram N-Methyl pyrrolidone.After three hours, content filters through a Buchner funnel with form of suspension in the crystallizer, collects a pure anthracene and 177 grams contain N-Methyl pyrrolidone filtrate.With three parts of pure methyl alcohol, 120 milliliters every part washing anthracene pieces.Obtain at last 14 the gram purity be that 96.3%(calculates with every part of anthracene, its productive rate theoretical value 66.2%) anthracene.Vacuum distilling filtrate is also reclaimed 119 gram N-Methyl pyrrolidone.
Claims (9)
1, the method of separation and purification anthracene from coal tar raw material by crystallization and solid-liquid-extraction process, it is characterized in that carbolineum is cooled off in the cooling surface temperature is lower than 80 ℃ vertical mold, separate Residual oil, formed crude anthracene crystallization is used N-Methyl pyrrolidone in same crystallizer, N-methyl-hexanolactam, N, the N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, the N-methylformamide, the non-proton dipolar nature solvent treatment such as mixture of N-N-formyl morpholine N-or they and water, solvent load is the 40-250% (weight) of crude anthracene crystallization content, temperature is 20-60 ℃, then after filtration, centrifugal or any other currently known methods is isolated the purifying anthracene from its suspension, reclaim solvent and also reuse in technology.
2, the process of claim 1 wherein that the operation at crystallizer internal cooling carbolineum should repeat several times, half is full of crystal at least until the crystallizer internal volume.
3, claim 1 or 2 method, wherein the carbolineum cooling is carried out under 0-70 ℃ of lasting 2-20 hour condition.
4, the process of claim 1 wherein to be separated under the action of gravity and carry out.
5, the process of claim 1 wherein that isolated crystallization needs to have used the non-proton dipolar nature solvent wash of one or many with treating processes earlier from pure anthracene, and then use the low boiling-point and polarity solvent wash, and dry.
6, the method for claim 5 is wherein used methyl alcohol, ethanol, water or their mixture, and the mixture of water and acetone or methylethylketone is used as the pure anthracene of low boiling-point and polarity solvent wash.
7, the process of claim 1 wherein that the recovery of non-proton dipolar nature solvent is by vacuum distilling and by means of coming periodically purifying with the dilution of 1: 1 weight ratio of water, and by filter, the solid phase of centrifugal and other currently known methods precipitation separation.
8, the process of claim 1 wherein to use and a kind ofly be the 5-20 millimeter by its inside diameter ranges of bundle, the tubular metal crystallizer that the space can be made up of water or saline flow refrigerative metal tube in the pipe.
9, the process of claim 1 wherein that carbolineum needs to filter in advance by a kind of filtration adjuvant or a kind of slit strainer that can outside remove separate piece.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL1988276093A PL158769B1 (en) | 1988-11-30 | 1988-11-30 | Method isolating and purifying antracene of chemistry-of-coke origin |
| PLP-276093 | 1988-11-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1043309A CN1043309A (en) | 1990-06-27 |
| CN1025183C true CN1025183C (en) | 1994-06-29 |
Family
ID=20045247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89108882A Expired - Fee Related CN1025183C (en) | 1988-11-30 | 1989-11-30 | Method for isolation and purification of coal tar-derived anthracene |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH02199192A (en) |
| KR (1) | KR0157405B1 (en) |
| CN (1) | CN1025183C (en) |
| PL (1) | PL158769B1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19613497C1 (en) * | 1996-04-04 | 1997-11-13 | Vft Ag | Distillation process to improve the production of pure products from raw anthracene |
| WO2006022195A1 (en) * | 2004-08-23 | 2006-03-02 | Semiconductor Energy Laboratory Co., Ltd. | Method for purifying material comprising organic semiconductor, method for purifying material comprising pentacene, semiconductor device, and method for fabricating the semiconductor device |
| JP2006093668A (en) * | 2004-08-23 | 2006-04-06 | Semiconductor Energy Lab Co Ltd | Purification method for organic semiconductor and semiconductor device |
| CN100575957C (en) * | 2005-12-19 | 2009-12-30 | 中国矿业大学 | The dissolving and the component analysis method thereof of oil cinder |
| KR100894785B1 (en) * | 2006-12-29 | 2009-04-24 | 주식회사 효성 | Method and apparatus for the continuous crystallization separation and purification of high purity 2,6-dimethylnaphthalene |
| JP5987149B2 (en) * | 2012-02-24 | 2016-09-07 | 学校法人 中央大学 | Manufacturing method of organic EL element |
| CN104447181A (en) * | 2014-11-17 | 2015-03-25 | 宁夏中远天宇科技有限公司 | Novel extraction procedure in production process of refined anthracene |
| CN105505453B (en) * | 2016-01-15 | 2017-12-08 | 深圳前海新域能源科技有限公司 | A kind of coal tar is without the demetallated method of water desalination |
| CN105693459B (en) * | 2016-03-08 | 2018-09-21 | 曲靖众一精细化工股份有限公司 | A kind of technique of rotary drum purification anthracene |
| CN113024346B (en) * | 2021-03-19 | 2023-01-10 | 浙江大学衢州研究院 | Separation method of mixture of anthracene and pentanization reaction product thereof |
-
1988
- 1988-11-30 PL PL1988276093A patent/PL158769B1/en unknown
-
1989
- 1989-11-30 JP JP1312253A patent/JPH02199192A/en active Pending
- 1989-11-30 KR KR1019890017586A patent/KR0157405B1/en not_active IP Right Cessation
- 1989-11-30 CN CN89108882A patent/CN1025183C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR0157405B1 (en) | 1998-12-01 |
| PL158769B1 (en) | 1992-10-30 |
| KR900007765A (en) | 1990-06-01 |
| PL276093A1 (en) | 1990-06-11 |
| JPH02199192A (en) | 1990-08-07 |
| CN1043309A (en) | 1990-06-27 |
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