CN1957061A - Method for the production of bitumen from tar and the distillates thereof by oxidative thermal treatment - Google Patents
Method for the production of bitumen from tar and the distillates thereof by oxidative thermal treatment Download PDFInfo
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- CN1957061A CN1957061A CNA2005800117917A CN200580011791A CN1957061A CN 1957061 A CN1957061 A CN 1957061A CN A2005800117917 A CNA2005800117917 A CN A2005800117917A CN 200580011791 A CN200580011791 A CN 200580011791A CN 1957061 A CN1957061 A CN 1957061A
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- 238000007669 thermal treatment Methods 0.000 title claims abstract description 20
- 239000010426 asphalt Substances 0.000 title claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims description 30
- 239000000203 mixture Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000011280 coal tar Substances 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 5
- 239000010439 graphite Substances 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 238000005194 fractionation Methods 0.000 claims description 30
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 6
- 230000011218 segmentation Effects 0.000 claims description 6
- 206010021143 Hypoxia Diseases 0.000 claims description 5
- 239000007833 carbon precursor Substances 0.000 claims description 5
- 239000003205 fragrance Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000001146 hypoxic effect Effects 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003570 air Substances 0.000 abstract 1
- 239000003245 coal Substances 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000011295 pitch Substances 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 15
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 14
- 239000011269 tar Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 241000254158 Lampyridae Species 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KCOYLRXCNKJSSC-UHFFFAOYSA-N 9h-carbazole Chemical group C1=CC=C2C3=CC=CC=C3NC2=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 KCOYLRXCNKJSSC-UHFFFAOYSA-N 0.000 description 1
- IHICGCFKGWYHSF-UHFFFAOYSA-N C1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1C Chemical class C1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1C IHICGCFKGWYHSF-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FMMWHPNWAFZXNH-UHFFFAOYSA-N ERM-AC051 Natural products C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- -1 useful at electrode Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/04—Working-up tar by distillation
- C10C1/16—Winning of pitch
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Working-Up Tar And Pitch (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the production of asphaltum from distillates arising from high temperature coal tar having a distillation range of more than 260 DEG C, by means of sequential and combined application of three stages in mild pressure and temperature conditions (<400 DEG C, <10 bar g), oxidative thermal treatment used as a reagent for air or oxygen, mixtures thereof, or air which is low in oxygen, thermal treatment in an inert atmosphere and fractionated distillation. It is possible to obtain asphaltum exhibiting environmental advantages and advantages in term of occupational health, which can be used as coal precursors, manufacturing of cathode/anode for aluminum industry, electrodes, common composite graphite, bonds for refinery industry and waterproofs.
Description
Technical field
The present invention generates pitch about a kind of from coal tar, more particularly is applicable to the method for making as pitch and other product of distillation of carbon precursor, by following three steps of an order combination operation:
1. reaction: the oxidizing thermal treatment under the condition of moderate pressure and temperature (＜400 ℃,＜10bar g, operating time scope 2-10 second, more preference 350-400 ℃, 5-10bar g, 6-10 second), use air, oxygen, hypoxic air or its mixture as reagent.
2. the oxidizing thermal treatment under inert atmosphere (340-400 ℃,＜10bar g, operating time scope 3-10 second, more preference 370-400 ℃, barometric point, 4-6 hour) is in order to make the stable of reaction product.
3. stepwise distillation (preference in a vacuum or with steam or rare gas element stripping) with according to palpus should be used for regulating the softening temperature (softening point) of pitch or carbon precursor.
Background technology
Pitch is generated by coal tar mostly, coal tar once dehydration and from BTX (＜5%, after first lighting end Benzene-Toluene-Xylenes) was shifted out, it caused that other fractionation that continues is according to different fractionation stage:
The naphtalene oil fractionation:, and have in the operation greater than 50% naphthalene content less than 260 ℃ in a fractionation scope, its representative is used with generation near 20% parent tar the naphthalene composition of height economic worth and the science and technology product with oil.
Carbolineum fractionation: in 260-400 ℃ of operation of a fractionation scope, the compounding mixture of the fragrant hydrocarbon polymer of one poly-cyclophane is by anthracene (anthracene), luxuriant and rich with fragrance (phenanthrene), firefly anthracene (Fluoranthene), pyrene (pyrene)., carbazole (Carbazole) forms, its representative becomes the product that directly sells near 30% parent tar can have strong competitive power in order to produce carbon black in various oil residuums.The pitch that converts thereof into the main part in this segmentation distillation simultaneously has the coml interests.
Pitch: it is maximum products of gained from the tar fractionation, is softening temperature 30-250 ℃ black solid, is characterized as the material that comprises such as toluene and quinoline and is not dissolvable in water in some solvent.It has three or more condensation aromatic nucleus for the compounding mixture of the fragrant hydrocarbon polymer of poly-cyclophane, and representative is near 50% parent tar.It is to make one of employed raw material of electrode in aluminium and the graphite industry.
Because make the separation that only comprises oils in the bituminous method, up to the adjustment that has before had tar medium pitch softening temperature.The production of its method can be considered as a simple physical operations relatively, and therefore, the asphalt quality of being obtained by located by prior art can be because the coal-tar middle oil quality of method for making has classification.
Coal tar is a product that very easily becomes for these characteristics of by product from carbon battery make this raw material, and this shortcoming can only be filled a prescription through suitable tar hotchpotch and be remedied.In any situation, the tar of all forms with the pitch of next obtaining, all has solid particulate and suspends (main and less important QI, and mist), the metal mud that follow different shape, can be differentiated by its ash composition.Two kinds of pollutents injure the bituminous qualities and/or reduce its application possible in the high-order carbon material.
Obtain separately in the fractionation of carbolineum by coal tar, and comprise the 260 ℃ of relative temperatures to the adjustment pitch softening point of having an appointment in its fractionation scope especially, this pitch is as the finished product (being generally 400-410 ℃).The carbolineum major part is made of the aromatic hydrocarbon of 2-4 phenyl ring, and heterogeneous ring compound, phenanthrene, anthracene, firefly anthracene, carbazole, pyrene that its correspondence has oxygen, nitrogen and sulphur are main constituent.The carbolineum of height aromatize, all can complete fractionation as the feature of a fractionation product and its four corner, these characteristics can be changed the raw material that this product becomes highly consistent quality, the possibility that allows it have more refinings to use.
Many aromatic hydrocarbons in carbolineum and some heterogeneous ring compounds are converted into anisotropy and the graphited carbonaceous material of energy, moderately pressurize in a closed tube to avoid volatilization by being heat-treated to 1000 ℃ at a slow speed.Though being heat-treated to a low temperature can suspend at one intermediate stage-pitch-productive rate very low.Comprise a dehydrogenation fragrance condensation that is produced by the free radical method in this method for making.This generation bituminous intermediate steps is still carried out extreme high temperature and suitable the hanging down under the turnover ratio that is used for the industry stage.These have all advised bringing out the possibility of fragrant condensation, by the generation of catalyzed reaction increase free radical, also have low temperature condensation and dehydrogenation reaction by low-yield to generate.May bringing out between the body of the reaction of these types, catalyzer such as Friedel-Craft (BF
3/ HF, AlCl
3) and sulphur be known.For quality or the reason of running cost and the residuum/byproduct of generation of the finished product, this kind catalyzer is also inappropriate, therefore advises the present invention and constitutes target, uses oxygen, air, hypoxic air or its mixture in reaction.
In tar and the bituminous air handling, with matrix material, synthetic liquid crystal (mesophase) and fiber are actually used in different purposes as increasing molecular weight and raising tar and bituminous softening temperature, avoiding the expansion of composite carbon/carbon material automatically, with fiber thermostabilization before the carbonization etc., be to generate at bituminous but there is not this similar carbolineum to handle.
The patent EP-A-0167046 of European Union discloses in a kind of fractionation fraction (distillation fraction) by coal tar or its deutero-heavy oil, for contain the generation method of low composition solid bitumen by the air or oxygen oxidation, when it is heated to temperature 315-385 ℃ an of preference, though the possibility of mentioning low temperature (149 ℃) operation is arranged, up to obtain one need intermediate product.Sent to fractionation by steam or rare gas element stripping after this intermediate product, though this fractionation can be avoided by use high temperature in oxidation mutually, its result obtains a dipping agent bitumen (impregnating pitch) that is used in particular for making electrode.
Importing an intermediate heat treatment does not see before with the possibility of promoting asphalt quality (aspect rheology project and fixed carbon) and ultimate yield and states patent.Pressure condition in this recipe step or required time are not mentioned in this patent yet.
Summary of the invention
According to method for making of the present invention, compared to prior art, it starts from a raw material in a big way, includes petrochemical industry fragrance fraction.The pitch of invention gained according to this, when the pitch in prior art, it presents a higher built-in quality and about the improvement characteristic of healthy (carinogenicity) and environment.
Carbolineum and temperature are lower than 400 ℃ and are higher than the reaction of oxygen in 350 ℃ the air with preference, and it sees through a mechanism allows the major ingredient of carbolineum react producing the condensation of molecule again, this mechanism show be similar in appearance to when sulphur as catalyzer presented.
The change that is found to parameter such as temperature, operating time, air-flow (air/oxygen) and reactor pressure is by promoting or suppress fragrant condensation reaction and influential on response path that its formation for the compatible molecule structure (compatible molecular structure) that can promote fragrant condensation reaction replacement polymerization or crosslinking reaction has key.The planarity that one extra heat treatment under inert atmosphere can increase molecule with stablize this reaction product, filter out possible side reaction, this thermal treatment further promotes its wettability, increases its graphite voltinism and generally improves reaction yield.
Be presented at actual minimizing on the carcinogenic composition according to the pitch that the present invention produced, it is to cause because the restriction of pitch in carbolineum exists content and the operational condition that sees through suggestion to reach reaction institute.
Its simultaneously, the fractionated performance of segmentation is accompanied by the molecular weight of being reached by the selectivity operational condition and distributes in the vacuum, produces the pitch with low volatility, low volatility represents one in fact to the advantage of environment.
The reaction of carbolineum and air only produces water includes hypoxic air, carbon monoxide and carbonic acid gas as by product/effluent (slightly being subjected to the pollution of ammonia and the ammoniacal liquor that composition is equal to gained in the tar fractionation process) and air-flow.Because do not have solid particulate and metal mud in pitch and the carbonaceous material, so final product does not have this a little materials.
According to selected reaction conditions, last pitch can produce its arriving of can observing of coke under the opticmicroscope of polarity light, according to the bituminous characteristic can present 100% anisotropic or 100% etc. the tropism.
According to pitch that method for making of the present invention produced aspect the favourable characteristic, these pitches are applicable to the field application of carbon precursor, particularly useful at electrode, Graphite Electrodes and the general composite electrode of making aluminium industry, cakingagent, water-proof material and the electrometallurgy colloid of refining industry.
Because the low selectivity of reaction, unreacted carbolineum may directly be peddled, and cooperates the aforementioned general application of being done by tar fractionation gained raw material.Relatively, become the anthracene/luxuriant and rich with fragrance condensation of the composition that is inferior to reaction, its increase can be provoked the fractionation stage that anthracene colloid substantial benefit is made in this promotion.
In method for making, avoid that deutero-phenomenon state is produced by side reaction for three kinds:
1. crosslinking structure/colloidal forms.
2. the generation of solid particulate.
3. the formation of high molecular structure.
The condition of method for making maximizes productive rate, economy and the security of method for making simultaneously by determining for fear of aforesaid side reaction.For this reason, selected following parameter:
● temperature 250-400 ℃, preference 350-400 ℃
● pressure: 5-10bar g
● particular airflow (21% oxygen): the every kg carbolineum of 0.1-0.25kg/
● the operating time during reaction: 2-10 second, preference 6-10 second
● one step conversion :≤40%, by reaching 60% or higher clean productive rate in the switch process of success
● the thermal treatment in the rare gas element: 340-400 ℃; 3-10 hour; 0-10bar g, preference 370-400 ℃;
Barometric point; 4-6 hour.
● fractionation is to softening temperature: according to the present invention, temperature range 85-250 ℃, detected by the testing method of the Mettler gilsonite softening temperature that is used to commonly use application.
According to the present invention, method for making sees through three steps of applied in any combination in regular turn and implements:
● oxidizing thermal treatment (reaction)
● the thermal treatment in the rare gas element (stablizing)
● very aerial segmentation fractionation (regulate softening temperature and consume volatile component)
Therefore obtain pitch, compared to by the pitch in the standard method for making, can give the standard method for making of about 50% productive rate as EP-A-0167046, this pitch can be used for multiple application and improving to some extent on healthy (carcinogenic substance composition) and environment (volatile component) correlation properties.
Description of drawings
For foundation the invention process method for making, though there is not the form of combination or restriction, its major program program is as subsidiary Fig. 1 explanation, and parameter wherein out of the ordinary is indicated:
1. reactor
2. come and go the group Pu
3. agent delivery system (air/oxygen)
4. static mixer
5. oxygen analyzer
6. heat-treating modules body
7. the fractional column regulated of softening temperature
8. pressure-regulator
9. thermoswitch
10. heating system
11. exhaust system
12. carbolineum inlet
13. scavenge system
14. the circulation of unreacted carbolineum
15. pitch outlet
Embodiment
The following example is relevant to specific embodiments of the invention, but does not cause any restricted feature.
As the preference raw material that uses, the carbolineum that is come by the coal tar fractionation has following average characteristics (nonrestrictive aspect)
| Raw material: carbolineum | |
| Origin | The high temperature tar fractionation |
| Fractionation scope (BS144) | ＞260℃ |
| Density (ASTM D1298) | ＞1.120g/cm 3(20℃) |
| Ash (ASTM D482) | ＜0.02％ |
| Insoluble toluene (BS144) | ＜0.1％ |
| C/H atomic ratio (ASTM D5291) | ＞1.30 |
According to the advantage feature among the present invention, different carbon geochemistry fractionation can be by enlarging or dwindle the fractionation scope of suggestion and use, and be not unfavorable for the product quality.The single important change product that can get will be in method for making by higher or obtain than deriving in the low-yield.
When using non-carbon geochemistry oils or have a large amount hetero atom (heteroatoms) composition, and/or have an a large amount naphthalene structure composition and a cross chain, reaction must careful guiding to avoid the shaping of colloid and crosslinked structure.The feasible practice is converted to an one step for increasing temperature and reduction.
Embodiment one:
Be in following condition, to handle the one-carbon chemical oil sample originally in above-mentioned main planning:
● temperature: 350 ℃
● the operating time: 6 seconds
● particular airflow: 60Nl/h air/every kg oil
● pressure: 5bar g
● thermal treatment: 400 ℃; 5 hours; 10bar g
● fractionation: be adjusted to 90 ℃ of Mettler softening temperatures
Therefore obtain pitch, have following feature, and the clean productive rate of bituminous is as 55% compared to dipping pitch by standard.
| Parameter | Unit | Embodiment one | Standard asphalt |
| Softening temperature (ASTM D3104) | ℃，Mettler | 90 | 90 |
| Flash point (ASTM D92) | ℃，COC | 274 | 250-270 |
| Soluble toluene (ISO 6376) | ％ | 29.5 | 15.0 |
| Soluble quinoline (ASTM D2318) | ％ | 1.0 | 0.8 |
| The Beta-resin | ％ | 28.5 | 14.2 |
| Fixed carbon (CRDG-B10) | ％，Sers | 44.7 | 40.1 |
| Filterability | g，80min | 43.3(6min) | 15-20 |
| Ash (ASTM D2415) | ％ | ＜0.01 | 0.1 |
See through the measurement that filtering rate and beta-resin and fixed carbon increase, what the essence increase in the pitch that obtains at last on the rheological property can be observed arrives.
Embodiment two:
In above-mentioned main planning, it is to handle a carbolineum sample in following condition:
● temperature: 350 ℃
● the operating time: 4 seconds
● particular airflow: 60Nl/h air/every kg carbolineum
● pressure: 5bar g
● thermal treatment: 400 ℃; 5 hours; 10bar g
● fractionation: be adjusted to 90 ℃ of Mettler softening temperatures
Therefore obtain pitch, have following feature, and the clean productive rate of bituminous is as 38% compared to dipping pitch by standard.
| Parameter | Unit | Embodiment two | Standard asphalt |
| Softening temperature (ASTM D3104) | ℃，Mettler | 90 | 90 |
| Flash point (ASTM D92) | ℃，COC | 276 | 250-270 |
| Soluble toluene (ISO 6376) | ％ | 25.3 | 15.0 |
| Soluble quinoline (ASTM D2318) | ％ | 0.4 | 0.8 |
| The Beta-resin | ％ | 24.9 | 14.2 |
| Fixed carbon (CRDG-B10) | ％，Sers | 43.1 | 40.1 |
| Filterability | g，80min | 59(6min) | 15-20 |
| Ash (ASTM D2415) | ％ | ＜0.01 | 0.1 |
A control and a higher temperature of reaction (being relevant to embodiment one) of observing conversion in the present embodiment provide one to have the product that increases filterability and low soluble quinoline, the result is the low output of a crosslinking structure, this crosslinking structure is a high-molecular weight compounds, and therefore the less time that is embodied as of method for making produces with low solid.
Embodiment three:
In above-mentioned main planning, it is to handle a carbolineum sample in following condition:
● temperature: 350 ℃
● the operating time: 4 seconds
● particular airflow: 60Nl/h air/every kg carbolineum
● pressure: 5bar g
● thermal treatment: 400 ℃; 5 hours; 10bar g
● fractionation: be adjusted to 110 ℃ of Mettler softening temperatures
Therefore obtain pitch, have following feature, and the clean productive rate of bituminous is as 35% compared to dipping pitch by standard.
| Parameter | Unit | Embodiment three | Standard asphalt |
| Softening temperature (ASTM D3104) | ℃，Mettler | 110 | 110 |
| Volatility (ASTM D2569) | ％a 360℃ | 0.0 | 0.3 |
| Soluble toluene (ISO 6376) | ％ | 29.2 | 29.0 |
| Soluble quinoline (ASTM D2318) | ％ | 1.3 | 10.0 |
| The Beta-resin | ％ | 27.9 | 19.0 |
| Fixed carbon (CRDG-B10) | ％，Sers | 49.0 | 54.0 |
| Degree of wetting (CRDG SERS) | ℃，Goutte | 137 | 134 |
| Ash (ASTM D2415) | ％ | ＜0.01 | 0.1 |
| B[a]P equiv. | g/kg，EPA | 18 | 28 |
In the present embodiment, the pitch that obtains at last can be suitable as the pitch of electrode usefulness cakingagent in the aluminium industry.When soluble quinoline ratio that need be higher, may prepare highly soluble composition and one-carbon chemical bituminous mixture, in this example, obtain one and have the beta resin of improvement and the pitch of fixed carbon (being standardized to a soluble stage) parameter.
Can offset and be used for producing and have low composition carcinogenic substance (B[a] P equiv.) and potential advantage during than the carbon precursor of low environmental impact (volatile component when not having 360 ℃) by above-mentioned characteristic.
Embodiment four:
In above-mentioned main planning, it is to handle a carbolineum sample in following condition:
● temperature: 350 ℃
● the operating time: 4 seconds
● particular airflow: 60Nl/h air/every kg carbolineum
● pressure: 5bar g
● thermal treatment: do not have
● fractionation: be adjusted to 90 ℃ of Mettler softening temperatures
Therefore obtain pitch, have following feature, and the clean productive rate of bituminous is as 35% compared to dipping pitch by standard.In the following table that has a further comparison purpose, also disclose, the sample among the embodiment two as the data of a reference to show the benefit of the intermediate heat treatment of being advised among the present invention.
| Parameter | Unit | Embodiment three | Standard asphalt | Embodiment four |
| Softening temperature (ASTM D3104) | ℃，Mettler | 90 | 90 | 90 |
| Flash point (ASTM D92) | ℃，COC | 276 | 250-270 | 272 |
| Soluble toluene (ISO 6376) | ％ | 25.3 | 15.0 | 23.8 |
| Soluble quinoline (ASTM D2318) | ％ | 0.4 | 0.8 | 0.5 |
| The Beta-resin | ％ | 24.9 | 14.2 | 23.3 |
| Fixed carbon (CRDG-B10) | ％,Sers | 43.1 | 40.1 | 42.0 |
| Filterability | g，80min | 59(6min) | 15-20 | 67(55min) |
| Ash (ASTM D2415) | ％ | ＜0.01 | 0.1 | ＜0.01 |
Can be observed the heat treated operation of a stabilization in the present embodiment and how to promote filterability (rheological property).Its while, the variation of thermal treatment in beta resin, fixed carbon and overall productivity influence.
Claims (8)
1. method for making that generates pitch and product of distillation thereof from coal tar, it is characterized in that this method for making is by three steps enforcements under moderate pressure and temperature control, these steps are: use oxidizing thermal treatment, the thermal treatment under the inert atmosphere and the segmentation fractionation of reagent air, oxygen, hypoxic air or its mixture.
2. as the method for making in the claim 1, it is characterized in that: this oxidizing thermal treatment implementation condition for temperature less than 400 ℃, pressure less than 10bar g and operating time in scope 2-10 second, and preference 350-400 ℃, 5-10bar g and 6-10 use thermal treatment and segmentation fractionation under reagent air, oxygen, hypoxic air or its mixture, the inert atmosphere second.
3. as the method for making in claim 1 and 2, it is characterized in that: the oxidizing thermal treatment implementation condition under this inert atmosphere for temperature less than 340-400 ℃, pressure less than 10bar g and operating time at scope 3-10 hour, and preference 370-400 ℃, barometric point and 4-6 hour be with the stopping reaction product, and its result is the gained bituminous quality of high yield and improvement.
4. as the method for making in the claim 1,2 and 3, it is characterized in that: this segmentation fractionating step implementation condition is that preference is in vacuum or by rare gas element or steam stripping, to regulate the bituminous softening temperature.
5. as the method for making in the claim 1,2,3 and 4, it is characterized in that: the carbolineum of its gained has the anthracene of increase/luxuriant and rich with fragrance concentration.
6. as the use of the pitch of method for making gained in the claim 1 to 4, it is especially at the carbon precursor of high-order.
7. as the use of the pitch of method for making gained in the claim 1 to 4, be used for electrode, Graphite Electrodes (as cakingagent pitch or a dipping agent bitumen) and general synthetic graphite, the cakingagent that be used to refine industry, water-proof material and the electrometallurgy colloid of manufacturing needles for aluminium industry.
8. as the making of the byproduct carbolineum of method for making gained in the claim 5, be with its manufacturing in anthracene glue.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ESP200400421 | 2004-02-20 | ||
| ES200400421A ES2238931B1 (en) | 2004-02-20 | 2004-02-20 | PROCEDURE FOR OBTAINING BREAS FROM ALQUITRANES AND ITS DISTILLATES FROM THE HULLA RENTAL, THROUGH OXIDATIVE THERMAL TREATMENT. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1957061A true CN1957061A (en) | 2007-05-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800117917A Pending CN1957061A (en) | 2004-02-20 | 2005-02-17 | Method for the production of bitumen from tar and the distillates thereof by oxidative thermal treatment |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1739153B1 (en) |
| JP (1) | JP2007525578A (en) |
| KR (1) | KR20070044800A (en) |
| CN (1) | CN1957061A (en) |
| AT (1) | ATE523579T1 (en) |
| BR (1) | BRPI0507215B1 (en) |
| CA (1) | CA2556482C (en) |
| DK (1) | DK1739153T3 (en) |
| ES (2) | ES2238931B1 (en) |
| PL (1) | PL1739153T3 (en) |
| WO (1) | WO2005079136A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111518583A (en) * | 2020-04-20 | 2020-08-11 | 华中科技大学 | Solid waste pyrolysis liquid phase product fused salt gradient treatment impurity removal and quality improvement device |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0800466B1 (en) * | 2008-03-05 | 2016-05-17 | Saint Gobain Cerâmicas & Plásticos Ltda | process of developing an ecological bonding system for a refractory mass |
| US8747651B2 (en) * | 2008-05-22 | 2014-06-10 | Graftech International Holdings Inc. | High coking value pitch |
| RU2477744C1 (en) * | 2011-11-29 | 2013-03-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Method for obtaining oil pitches |
| JP6076147B2 (en) * | 2013-03-11 | 2017-02-08 | 株式会社クレハ | Manufacturing method of high softening point pitch |
| KR102207835B1 (en) * | 2013-12-23 | 2021-01-26 | 재단법인 포항산업과학연구원 | Method for preparing pitch for carbon material using coal tar distillate and pitch for carbon material prepared by the same |
| CN108003910B (en) * | 2016-10-27 | 2020-06-19 | 宝武炭材料科技有限公司 | Preparation method of high-softening-point environment-friendly asphalt, asphalt and application |
| CN107446606B (en) * | 2017-08-30 | 2024-01-23 | 西北大学 | Process and device for producing modified asphalt, aliphatic hydrocarbon and aromatic hydrocarbon from coal tar |
| KR102202219B1 (en) * | 2018-12-13 | 2021-01-12 | 재단법인 한국탄소융합기술원 | Method for densifying carbon block |
| US11248172B2 (en) | 2019-07-23 | 2022-02-15 | Koppers Delaware, Inc. | Heat treatment process and system for increased pitch yields |
| RU2744579C1 (en) * | 2020-06-01 | 2021-03-11 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Method for obtaining binding pitch |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146048A (en) * | 1977-05-02 | 1979-03-27 | Prefco Productions, Inc. | Fire damper and method of fabrication |
| GB2115437B (en) * | 1982-02-15 | 1985-10-02 | Nippon Oil Co Ltd | Pitch for carbon fibers |
| US4664774A (en) * | 1984-07-06 | 1987-05-12 | Allied Corporation | Low solids content, coal tar based impregnating pitch |
| US4892642A (en) * | 1987-11-27 | 1990-01-09 | Conoco Inc. | Process for the production of mesophase |
-
2004
- 2004-02-20 ES ES200400421A patent/ES2238931B1/en not_active Expired - Fee Related
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2005
- 2005-02-17 BR BRPI0507215-8A patent/BRPI0507215B1/en active IP Right Grant
- 2005-02-17 PL PL05708091T patent/PL1739153T3/en unknown
- 2005-02-17 ES ES05708091T patent/ES2376938T3/en active Active
- 2005-02-17 KR KR1020067018337A patent/KR20070044800A/en not_active Application Discontinuation
- 2005-02-17 DK DK05708091.3T patent/DK1739153T3/en active
- 2005-02-17 CN CNA2005800117917A patent/CN1957061A/en active Pending
- 2005-02-17 WO PCT/ES2005/000079 patent/WO2005079136A2/en active Application Filing
- 2005-02-17 AT AT05708091T patent/ATE523579T1/en active
- 2005-02-17 JP JP2006553601A patent/JP2007525578A/en active Pending
- 2005-02-17 EP EP05708091A patent/EP1739153B1/en active Active
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111518583A (en) * | 2020-04-20 | 2020-08-11 | 华中科技大学 | Solid waste pyrolysis liquid phase product fused salt gradient treatment impurity removal and quality improvement device |
| CN111518583B (en) * | 2020-04-20 | 2021-03-05 | 华中科技大学 | Solid waste pyrolysis liquid phase product fused salt gradient treatment impurity removal and quality improvement device |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0507215B1 (en) | 2015-05-26 |
| DK1739153T3 (en) | 2012-01-09 |
| CA2556482A1 (en) | 2005-09-01 |
| WO2005079136A2 (en) | 2005-09-01 |
| JP2007525578A (en) | 2007-09-06 |
| BRPI0507215A (en) | 2007-06-19 |
| ES2238931B1 (en) | 2007-06-16 |
| WO2005079136A3 (en) | 2005-12-29 |
| ATE523579T1 (en) | 2011-09-15 |
| PL1739153T3 (en) | 2012-03-30 |
| ES2238931A1 (en) | 2005-09-01 |
| EP1739153A2 (en) | 2007-01-03 |
| CA2556482C (en) | 2012-11-27 |
| KR20070044800A (en) | 2007-04-30 |
| ES2376938T3 (en) | 2012-03-21 |
| EP1739153B1 (en) | 2011-09-07 |
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