CN1676583A - Medium-high-temperature coal tar hydro cracking process - Google Patents
Medium-high-temperature coal tar hydro cracking process Download PDFInfo
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- CN1676583A CN1676583A CN 200410043708 CN200410043708A CN1676583A CN 1676583 A CN1676583 A CN 1676583A CN 200410043708 CN200410043708 CN 200410043708 CN 200410043708 A CN200410043708 A CN 200410043708A CN 1676583 A CN1676583 A CN 1676583A
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- 239000011280 coal tar Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 16
- 239000003921 oil Substances 0.000 claims abstract description 45
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005336 cracking Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002737 fuel gas Substances 0.000 claims abstract description 15
- 239000002283 diesel fuel Substances 0.000 claims abstract description 13
- 238000005194 fractionation Methods 0.000 claims abstract description 10
- 239000010687 lubricating oil Substances 0.000 claims abstract description 4
- 239000000295 fuel oil Substances 0.000 claims description 37
- 239000003502 gasoline Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000003245 coal Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 238000004939 coking Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009874 alkali refining Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
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- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
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- 238000001819 mass spectrum Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 nitrogenous compound Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 238000009628 steelmaking Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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Abstract
This invention provides a medium and high temperature coal tar hydro-cracking technique. Lead medium and high temperature coal tar into heating furnace and mix it with hydrogen, and then the coal tar goes into the hydro-refining reactor and goes through high-pressure separator to get hydrogen that passes through cycle compressor to return to hydro-refining reactor, the formed oil goes into low-pressure separator to get low-fraction fuel gas and then goes into deoxiding tower to further remove the fuel gas and get into fractionation tower, and the fractionated petroleum, diesel oil and lubricating oil are led to the fractionation tower and the offal oil is led to cracking heating furnace to mix with hydrogen and then goes into the cracking reactor, and after the cracking reaction, the formed oil goes into low-pressure separator to get fuel gas and goes into fractionation tower to fractionate with hydro-refining oil. This invention converse the low-value and heavy-polluting coal tar into high grade petroleum, diesel oil and lubricating oil to reduce the environmental pollution.
Description
(1), affiliated field
What the present invention relates to is coal chemical technology, specifically a kind of middle coal-tar heavy oil hydrocracking process.
(2), background technology
The comprehensive utilization of centering coal-tar heavy oil resource is especially significant to environment protection.In today of petroleum resources growing tension, utilize coal and coal tar to produce the oil replacement product and just have more great social significance.Its essence is based on hydrocracking process, pass through engineering development, the suitable cracking conditions of research, removing of the component of environmental pollutions such as realization centering coal-tar heavy oil sulphur, nitrogen, oil fuel, lubricant base or cracking stocks such as the gasoline of production high-quality simultaneously, environmental protection, diesel oil, middle coal-tar heavy oil is one of product of coal coking and gas maked coal, in the coal-tar heavy oil research of producing oil fuel products such as gasoline, diesel oil by deep processing method, once received much attention and dropped into substantial contribution and manpower studies in the twentieth century 50-60 age.Because China is in grand celebration, ground such as Xinjiang find and the recovery of subterranean oil that petroleum products is as the very fast motor spirit that has replaced gelatin liquefaction, gasification and coking to produce of main energy sources.From twentieth century seventies, China's centering coal-tar heavy oil deep processing is produced the research of oil fuel products such as the gasoline, diesel oil of high-quality environment-friendly type and almost be nobody shows any interest in, until twentieth century end of the nineties, because the raising of environmental consciousness, the raising of oil Refining Technologies, people are to the raising of the understanding of petroleum resources, and the comprehensive utilization of coal and coal tar is just paid attention to by the knowledgeable people again.
At present, the needed coke major part of domestic steel-making enterprise is from coal coking, process of coking can produce a large amount of middle high temperature tars, the domestic in addition coking plant that many gasification plants is arranged and produce semicoke, but also different according to coal-tar heavy oil amount in the different by-products of the tar content of coal, middle coal-tar heavy oil output is more in the factory below 50,000 tons/year.The middle coal-tar heavy oil part of these coking plants and gasification plant by-product is directly burnt as low-quality fuel oil behind acid-alkali refining at present, or directly burn as emulsion fuel after the emulsification, impurity such as institute's sulfur-bearing, nitrogen become sulphur and nitrogen oxide and discharge into the atmosphere and cause topsoil in combustion processes, and produce large amount of sewage in the acid-alkali refining process again, a part is behind acid-alkali refining, and extraction separation goes out burnedly after the chemical substances such as phenol, naphthalene to fall or use as heating and culinary art.Coal institute sulfur-bearing like this, impurity such as nitrogen become sulphur and nitrogen oxide and discharge into the atmosphere and cause topsoil in combustion processes, coal combustion process also causes dust pollution, therefore, with the coal is that the raw material production town gas is more and more higher as the ratio of domestic fuel, the middle coal-tar heavy oil amount of association simultaneously also rolls up, and China's oil inadequate resource, the crude oil import ratio increases year by year, with middle coal-tar heavy oil is stock oil, adopt more suitable secondary processing means to produce clean fuel or the petroleum products suitable with petroleum products, not only have remarkable economic efficiency, also have obvious social simultaneously.
(3), summary of the invention
The object of the present invention is to provide a kind of quality productss such as gasoline, diesel oil that middle coal-tar heavy oil is changed into, the utility value of coal-tar heavy oil in the raising, the middle coal-tar heavy oil hydrocracking process of minimizing environmental pollution.
The object of the present invention is achieved like this: middle coal-tar heavy oil introduce process furnace be heated to 250-300 ℃ and with hydrogen be 1100-1300 by hydrogen to oil volume ratio: 1 mixed, enter hydrofining reactor after the mixing, enter high-pressure separator through heat exchange then, separate, separated hydrogen is got back to hydrofining reactor through recycle compressor, generate oil and enter light pressure separator, enter the deoxidation tower after isolating low branch fuel gas, enter separation column at 0.3～0.8Mpa after further taking off fuel gas, carry out fractionation under 280-340 ℃ the condition, gasoline after the fractionation, diesel oil and lubricating oil are drawn separation column, tail oil then introduce the cracking process furnace be heated to after 350-420 ℃ with hydrogen by hydrogen to oil volume ratio 700-900: enter cracking case after 1 the mixed, having under the condition of catalyzer, carry out cracking reaction, generation is than the lightweight oils and the fuel gas of small molecules, entering the high-pressure separator separated hydrogen then circulates by recycle compressor, generation oil then enters and enters separation column after light pressure separator is isolated fuel gas, generates oil with hydrofining and carries out fractionation.
The present invention can also comprise some features like this:
1, the hydrogen to oil volume ratio of hydrofining reaction is 1200: 1.
2, the hydrogen to oil volume ratio of cracking reaction is 800: 1, and temperature of reaction is 380 ℃.
3, the catalyzer of described cracking reaction is FC-28.
The present invention is a target with resource comprehensive utilization rationally and environmental protection, utilizes petroleum refining industry's modern technologies to improve the property transplanting to coal chemical technology, with in coal-tar heavy oil yield products of quality, the utility value of coal-tar heavy oil in the raising is protected environment.Key of the present invention is to utilize the hydrocracking process technology, adjusts the processing condition of hydrocracking process, the final purpose of coal-tar heavy oil upgrading in the realization.Because middle coal-tar heavy oil comes from coal coking and gasification retort section, is the thermally splitting product.The character of middle coal-tar heavy oil is very complicated, and their chemical constitution mainly is an aromatics, and alkane and olefin(e) centent are less, also contain and contain oxygen, nitrogenous, sulfocompound on a small quantity.Oxygenatedchemicals mainly is to have weakly acidic various corresponding phenolic, and nitrogenous compound mainly is to have weakly alkaline pyridine, and quinoline and their derivative, sulfocompound mainly are thiophene, mercaptan, thiophenol, thioether, thia indenes etc.By hydrocarbon hydrocracking reaction mechanism and middle coal-tar heavy oil cracking reaction feature and middle coal-tar heavy oil property analysis as can be known, such oily aromatic hydrocarbons, colloid, the asphalt content height, macromole chain hydrocarbon content is few, in temperature, pressure, under catalyzer and the hydro condition, sulfide in the middle coal-tar heavy oil, nitride, oxide compound respectively with the hydrogen generation hydrogen sulfide that reacts, ammonia and water, colloid and bituminous matter then generate micromolecular hydro carbons and coke, the macromolecule hydrocarbon of aromatic hydrocarbons and long-chain is then distinguished micromolecular hydro carbons saturated and cracking generation naphthenic hydrocarbon and short chain, finally reaches the purpose of upgrading.
Major advantage of the present invention is embodied in: the middle coal-tar heavy oil of low value, high pollution is changed into fine gasoline, diesel oil, lubricated wet goods, and the objectionable impurities in the middle coal-tar heavy oil can be deviate from, reduced environmental pollution to greatest extent.
(4), description of drawings
Accompanying drawing is a process flow diagram of the present invention.
(5), specific embodiments
For example the present invention is done more detailed description below:
In coal-tar heavy oil heater via 1 heating with enter hydrofining reactor 2 after hydrogen mixes, sulfide in hydrofining reactor in the oil, nitride and oxide compound generate hydrogen sulfide with hydrogen reaction respectively, ammonia and water are after heat exchange enters high-pressure separator 3, after isolating hydrogen, hydrogen is got back to hydrofining reactor through recycle compressor, generate oil and then enter light pressure separator 4, enter deoxidation tower 5 after isolating low branch fuel gas, enter separation column after further taking off fuel gas, in separation column 10, will generate oil content and be slit into gasoline, diesel oil and lubricant base and tail oil, tail oil is then by entering cracking case 7 after 6 heating of cracking process furnace with after hydrogen mixes, the macromolecular compound of the macromolecule hydrocarbon of long-chain and difficult reaction is further under the effect of cracking catalyst in cracking case, carry out cracking reaction, generation is than the lightweight oils and the fuel gas of small molecules, entering high-pressure separator 8 then isolates hydrogen and circulates by recycle compressor, generation oil then enters and enters separation column after light pressure separator 9 is isolated fuel gas, generate oil with hydrofining and carry out fractionation, thereby obtain gasoline, diesel oil, lubricant base and a spot of tail oil.
Different with the production purpose for example the main character of coal-tar heavy oil sees Table one to the described hydrocracking process of this patent in certain and different according to raw material, and the purpose product is a gasoline, diesel oil, the lube base oil production, processing condition see Table two, and the product main character sees Table three.
Table one: middle coal-tar heavy oil main character
Coal-tar heavy oil in the stock oil
Density (20 ℃), g/cm
31.0426
Boiling range, ℃
IBP/10％ 128/214
30％/50％ 291/357
70％/90％ 417/
95％/EBP 80％455
Viscosity (100 ℃), mm
2/ s 6.170
Condensation point, ℃ 26
Carbon residue, m% 5.40
Mechanical impurity, % 0.171
S，m％ 0.1606
N，m％ 0.8636
C，m％ 82.37
H，m％ 6.86
Metal content, μ g/g
Cu ＜0.01
Ca 27.5
Mg 4.70
Ni 0.76
V 0.12
Fe 46.39
Na 3.74
The compositional analysis data, m%
Paraffinic hydrocarbons 5.9
Naphthenic hydrocarbon 5.0
Aromatic hydrocarbons+colloid 89.1
Table two: hydrocracking process condition
The project condition
Refining project purification condition
The reaction stagnation pressure, MPa 128
Hydrogen to oil volume ratio 1200: 1
The protective material volume space velocity, 1.0
The protective material average reaction temperature, ℃ 240
Main finishing agent volume space velocity, h
-10.8
Main finishing agent average reaction temperature, ℃ 370
Generate the water yield, m% 9.12
Treated oil density, g/cm
30.885
The treated oil nitrogen content, μ g/g～100
Cracking project cracking conditions
The reaction stagnation pressure, MPa 128
Hydrogen to oil volume ratio, v 800: 1
The cumulative volume air speed, h
-10.8
Average reaction temperature, ℃ 380
＞370 ℃ of per pass conversion, m%～65
Table three: product main character
Numbering gasoline fraction diesel oil distillate tail oil cut
The cut scope, ℃＜180 180～370＞370
Density, g/cm
3(20 ℃) 0.7504 0.8652 0.8341
Boiling range, ℃
IBP/10％ 86/104 183/222
30％/50％ 111/121 248/273
70％/90％ 136/161 302/327
95％/EBP 171/186 337/344
Flash-point, ℃ 84
Condensation point, ℃-10
Cold filter clogging temperature, ℃
Carbon residue, m% 0.01
Octane value (cetane value) 75 36
Cetane index,
ASTM?D4737-96a 37
Mass spectrum is formed, %
Alkane 12.6 22.5 58.7
Naphthenic hydrocarbon 79.9 24.3 29.9
Aromatic hydrocarbons 7.5 53.2 11.4
Virtue dives 82.7
Sulphur content, μ g/g 8.3
Nitrogen content, μ g/g 4.8
Claims (5)
1, coal-tar heavy oil hydrocracking process in a kind of, it is characterized in that: middle coal-tar heavy oil introduce process furnace be heated to 250-300 ℃ and with hydrogen be 1100-1300 by hydrogen to oil volume ratio: 1 mixed, enter hydrofining reactor after the mixing, entering high-pressure separator through heat exchange then separates, separated hydrogen is got back to hydrofining reactor through recycle compressor, generate oil and enter light pressure separator, enter the deoxidation tower after isolating low branch fuel gas, enter separation column at 0.3～0.8Mpa after further taking off fuel gas, carry out fractionation under 280-340 ℃ the condition, gasoline after the fractionation, diesel oil and lubricating oil are drawn separation column, tail oil then introduce the cracking process furnace be heated to after 350-420 ℃ with hydrogen by hydrogen to oil volume ratio 700-900: enter cracking case after 1 the mixed, having under the condition of catalyzer, carry out cracking reaction, generation is than the lightweight oils and the fuel gas of small molecules, entering the high-pressure separator separated hydrogen then circulates by recycle compressor, generation oil then enters and enters separation column after light pressure separator is isolated fuel gas, generates oil with hydrofining and carries out fractionation.
2, middle coal-tar heavy oil hydrocracking process according to claim 1, it is characterized in that: the hydrogen to oil volume ratio of hydrofining reaction is 1200: 1.
3, middle coal-tar heavy oil hydrocracking process according to claim 1 and 2, it is characterized in that: the hydrogen to oil volume ratio of cracking reaction is 800: 1, temperature of reaction is 380 ℃.
4, middle coal-tar heavy oil hydrocracking process according to claim 1 and 2, it is characterized in that: the catalyzer of described cracking reaction is FC-28.
5, middle coal-tar heavy oil hydrocracking process according to claim 3, it is characterized in that: the catalyzer of described cracking reaction is FC-28.
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| CN 200410043708 CN1243814C (en) | 2004-07-14 | 2004-07-14 | Medium-high-temperature coal tar hydro cracking process |
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| CN 200410043708 CN1243814C (en) | 2004-07-14 | 2004-07-14 | Medium-high-temperature coal tar hydro cracking process |
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| CN1243814C CN1243814C (en) | 2006-03-01 |
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| CN100337747C (en) * | 2005-11-17 | 2007-09-19 | 中国石油化工集团公司 | Coal tar hydrogenating modification catalyst and its prepn and application |
| CN1876767B (en) * | 2006-06-28 | 2010-09-15 | 沈和平 | Coal tar hydrocracking method |
| CN101240191B (en) * | 2007-02-09 | 2011-08-24 | 中国石油化工股份有限公司 | Method for producing lightweight fuel oil by coal tar heavy fractioning hydrogenation |
| CN101041783B (en) * | 2006-03-21 | 2012-04-18 | 何巨堂 | Coal tar hydro-conversion method |
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2004
- 2004-07-14 CN CN 200410043708 patent/CN1243814C/en not_active Expired - Lifetime
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