CN1970690A - Fluidization hydrogenation liquefaction method for coal - Google Patents
Fluidization hydrogenation liquefaction method for coal Download PDFInfo
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- CN1970690A CN1970690A CN 200610151086 CN200610151086A CN1970690A CN 1970690 A CN1970690 A CN 1970690A CN 200610151086 CN200610151086 CN 200610151086 CN 200610151086 A CN200610151086 A CN 200610151086A CN 1970690 A CN1970690 A CN 1970690A
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- coal
- gas
- fluidization
- reactor
- hydrogenation liquefaction
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- 239000003245 coal Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000005243 fluidization Methods 0.000 title claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 22
- 239000003034 coal gas Substances 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000011280 coal tar Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000010883 coal ash Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000000428 dust Substances 0.000 abstract 2
- 239000011335 coal coke Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 5
- 238000002309 gasification Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000011269 tar Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 235000003642 hunger Nutrition 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000037351 starvation Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011286 gas tar Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a fluidization hydrogenating liquefying method of coal, which comprises the following steps: grinding coal; controlling the grain size of coal between 0.01 and 2000um with normal distribution; transmitting dust coal into hydrogenating liquefying reactor; using the composite gas of hydrogen or steam and carbon monodioxide to fluidize and hydrogenate the dust coal; aerating catalyst and auxiliary catalyst; cooling the coal gas and coke steam; separating coal gas from coal tar; transmitting oxygen and steam into hydrogenating reactor to transmit reacting residule into coal gas generator; making partial coal gas as heat carrier to blend with fresh coal ash into fluid-bed reactor.
Description
One, technical field
The object of the present invention is to provide a kind of working method of coal.Specifically a kind of method of liquefying coal.
Two, background technology
Worldwide in recent years studies show that, coal are that reserves are abundant but almost also not by the resource of fine utilization.An estimation of International Energy Agency shows that the future three of 2000-2030, China was as developing with present economic growth rate during the decade, and its increment energy demand will account for 20% of world's increment energy demand.We can say that the focus of following Chinese Economy Development is at the energy, energy strategy is the important component part of China's development strategy.The explored disposable energy reserve situation of just present China, China is an oil starvation, weak breath, and the abundant relatively country of coal resources, " oil starvation, weak breath, rich coal " is the fundamental realities of the country of China.Coal accounts for 94.3% in the fossil energy reserves of verifying, and oil and gas only accounts for 5.7%.3,800,000,000 tons of its PetroChina Company Limited.'s workable reserve can be adopted the time limit only 20 years, and Sweet natural gas total resources 38 tcms can be adopted and year be limited to 37 years.Imported oil was 1.2 hundred million tons in 2004, accounted for 41.67% of national oil consumption amount.Consumption of petroleum reached 3.2 hundred million tons in 2005, increased by 11% than the last year, and import surpasses 50%, and China has become the world's second largest oil consuming countries.Along with the crude oil demand of the constantly soaring and domestic cumulative year after year of International Crude Oil, domestic petroleum output can not satisfy the needs of national economy high speed development far away.Therefore, for guaranteeing the Sustainable development of Chinese national economy, optimize China's energy structure, reduction is to the interdependency of petroleum import, make full use of the coal resources advantage of China's abundant, greatly develop the Coal Chemical Industry new high-tech industry,, become the inevitable choice of China's energy strategy with Coal Chemical Industry products substitution petrochemicals.
The existing industrialization technology of handling coal be with it as fuel used to generate electricity, boiler oil, gasified raw material etc., the technology of researching and developing and researching and developing has: coking, gasification, low-temperature pyrolysis, Direct Hydrogenation liquefaction and indirect liquefaction etc.
1. coking: coal is placed gas retort, the secluding air heating, the organic rising with temperature is decomposed gradually in the coal, and wherein volatile matter is overflowed with gaseous state or vapor state, become coke-oven gas and coal tar, and the non-volatile solids residue is coke.
2. gasification: gasification is to change coal into can be used as industry or domestic fuel and chemical industry synthesis material coal gas.But it is that a kind of investment is very high that gasification is subjected to the restriction of the type of furnace, coal, moisture content, granularity, and gasification efficiency is not very high technology.
3. low-temperature pyrolysis: place coal under the temperature about 550 ℃ low-temperature pyrolysis can produce semi coking tar and coalitenessity producer gas.But produced simultaneously semicoke can not well obtain utilizing.
4. hydrogenation liquefaction: coal, catalyzer and solvent are in the same place, under High Temperature High Pressure, make destruction of organic material in the coal, be converted into low molecule liquid state and gaseous product with the hydrogen effect.But present coal liquefaction craft operating pressure MPa more than 20, temperature more than 460 degree, facility investment is quite high, and running cost is also quite big, and does not also have quite mature and stable industrialized unit at present.
5. indirect liquefaction: gasifying process and Fischer-Tropsch synthesis process combined produce low molecule liquid state and gaseous product.But this technology investment height at present, running cost is also high.
The patent that the fluidization of coal hydrogenation liquefaction is similar or close is not found in the patent inquiry.
Three, summary of the invention
The object of the present invention is to provide a kind ofly can become the macromole organic matter decomposition micromolecular organic matter, and can prevent to produce when the macromole organic matter decomposition from becoming the small molecules organic matter fluidization hydrogenation liquefaction method for coal of the material of more macromolecular similar coke effectively.
The object of the present invention is achieved like this: earlier blocky coal is pulverized, the powdery size-grade distribution after control is pulverized is normal distribution between the 0.01-2000 micron; Fine coal is sent into the hydrogenation liquefaction reactor, and the gas mixture that adds carbon monoxide with hydrogen or steam feeds catalyzer and promotor simultaneously to fine coal fluidisation hydrogenation; After coal gas that hydrogenator generates and the tarry vapours condensation cooling, isolate coal gas and coal tar; From hydrogenator reaction residues is sent into coal-gas producer with oxygen and water vapour, coal gas takes place, the coal ash part that coal gas taken place is mixed with fresh fine coal as thermal barrier and is sent into fluidized-bed reactor;
The present invention can also comprise some features like this:
1, described liquefaction of hydrogen reactor is a kind of in riser reactor, bubbling style fluidized-bed, dispersion fluidized bed, turbulent bed and fast bed reactor or the moving-burden bed reactor fluidized-bed reactor, and the best is a riser reactor.
2, to add the consumption of the gas mixture of carbon monoxide be 20-300 cubic meter/ton coal for hydrogen or steam.
3, described catalyzer is a Fe-series catalyst, and its consumption is 20-100 kilogram/ton coal.
4, described promotor is a hydrogen sulfide, and its consumption is 0.5-10 kilogram/ton coal.
5, described fluidized-bed reactor reaction conditions is: working pressure 0.05-6.0MPa, service temperature 380-560 ℃, gas-solid ratio 1.0-20: 1 (v/v).
Principle of the present invention is the fluidized-bed reaction principle.The powdery coal is under fluidized state, the gas mixture that adds carbon monoxide with high-temperature hydrogen or high-temperature steam is thermal barrier and fluidizing medium, feed a certain proportion of promotor simultaneously, with organic decomposition fast contained in the fine coal, replenishing hydrogen atom on the carbon-carbon bond of fracture fast simultaneously, make macromole contained in the coal organic decompose fast and again with the organic matter of active hydrogen atom synthesized micromolecule, finally leave reactor, and cool and isolate tar and coal gas through condensation with the form of tar steam.Reacted residue under the condition of aerating oxygen and water vapour, also produces coal gas in coal-gas producer, coal gas generates synthetic gas through workshop sections such as conversion again.
Key of the present invention be fine coal in fluidization hydrogenation liquefaction reactor with fine coal in contained most macromole organic matter all be decomposed into micromolecular organic matter, and the macromole organic matter constantly replenishes active hydrogen atom rapidly when decomposing, prevent to produce when the macromole organic matter decomposition from becoming the small molecules organic matter material of more macromolecular similar coke effectively, so just make the organic matter that contained originally in the fine coal almost entirely all become the small molecules organic matter, finally separate with the form and the fine coal of tar steam and coal gas.And reaction residues continues under the effect of oxygen and water vapour to produce the coal gas that carbon monoxide and hydrogen are formed in coal-gas producer, and coal gas then can be produced synthetic gas through workshop sections such as conversion as required.
Major advantage of the present invention is:
1. raw material availability 100%.
2. powdery fluidization of coal hydrogenation liquid carburetion yield height can reach the 150-350% of aluminium retort value.
3. coal gas can all take place in reaction residues, finally only surplus ash content, and the raw material that can be used as material of construction uses.
4. the liquid product of fluidization hydrogenation liquefaction is than the energy transformation ratio height of existing coal Hydrogenation liquefaction process, resource utilization height, comprehensive liquid yield height.Total liquid product yield is that about 3 tons of coals go out 1 ton of liquid product.
5. it is low to install operating pressure, only is equivalent to 1/3rd of direct liquefaction, operating safety, and reduced investment is equivalent to 1/3rd of direct liquefaction, and cost is low, is equivalent to 1/2nd of direct liquefaction.
Four, description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Five, concrete real-time mode
For a more detailed description to the present invention for example below in conjunction with accompanying drawing:
What accompanying drawing provided is process flow sheet of the present invention, 1--hydrogenator wherein, 2--fine coal storehouse, the 3--separation column, the 4--coal-gas producer, 5--catalyzer storehouse, 6--shift-converter, 7--fine coal, 8--coal gas and tarry vapours gas mixture, 9--coal gas, 10--heavy oil, the 11--reaction residues, 12--water vapour and oxygen mixture, coal gas, 14--catalyzer take place in 13--, the 15--coal ash, 16--high-temperature hydrogen (high-temperature vapour and carbon mono oxide mixture), 17--synthetic gas, 18--catalyzer, the 19--tar light oil, the 20--promotor.
At first will become the fine coal adding fine coal storehouse of 0-800 micron through two grade pulverization, adopt hydrogen that fine coal is transported in the hydrogenator then, select Fe-series catalyst, its consumption is selected between 20-100 kilogram/ton coal according to ature of coal, hydrogenator is selected riser reactor, the consumption of the gas mixture of hydrogen is 20-300 cubic meter/ton coal, its concrete add-on is selected according to ature of coal, also can replace hydrogen with the gas mixture of steam and carbon monoxide, working pressure 0.05-6.0MPa, service temperature 380-560 ℃.Feed hydrogen sulfide simultaneously, the consumption of hydrogen sulfide is selected between 0.5-10 kilogram/ton coal according to not coexisting of ature of coal.Under above-mentioned processing condition with the organic hydrogenation liquefaction in the coal.Reacted residue is sent in the coal-gas producer with the gas mixture of steam and oxygen, at reaction pressure 1.7Mpa, 750 ℃ of temperature of reaction, the processing condition of gas-solid ratio 4.5: 1 (v/v) issue the soft coal solid/liquid/gas reactions, enter the carbon monodixe conversion reactor then with the requirement of carbon monodixe conversion to synthesizing methanol gas, carbon monodixe conversion is adopted low--low unsteady flow journey.Hydrogenator top oil gas is sent in the separation column, obtains coal gas at the top of separation column, obtains light coal tar at the side line of separation column, obtains heavy oil in the bottom of separation column, and sends back in the hydrogenation liquefaction reactor.After the art of this patent processing, the finished product have: light coal tar, oil, methyl methanol syngas.
Claims (6)
1, a kind of fluidization hydrogenation liquefaction method for coal is characterized in that: earlier blocky coal is pulverized, the powdery size-grade distribution after control is pulverized is normal distribution between the 0.01-2000 micron; Fine coal is sent into the hydrogenation liquefaction reactor, and the gas mixture that adds carbon monoxide with hydrogen or steam feeds catalyzer and promotor simultaneously to fine coal fluidisation hydrogenation; After coal gas that hydrogenator generates and the tarry vapours condensation cooling, isolate coal gas and coal tar; From hydrogenator reaction residues is sent into coal-gas producer with oxygen and water vapour, coal gas takes place, the coal ash part that coal gas taken place is mixed with fresh fine coal as thermal barrier and is sent into fluidized-bed reactor.
2, fluidization hydrogenation liquefaction method for coal according to claim 1, it is characterized in that: described liquefaction of hydrogen reactor is a kind of in riser reactor, bubbling style fluidized-bed, dispersion fluidized bed, turbulent bed and fast bed reactor or the moving-burden bed reactor fluidized-bed reactor, and the best is a riser reactor.
3, fluidization hydrogenation liquefaction method for coal according to claim 1 is characterized in that: the consumption that hydrogen or steam add the gas mixture of carbon monoxide is 20-300 cubic meter/ton coal.
4, fluidization hydrogenation liquefaction method for coal according to claim 1 is characterized in that: described catalyzer is a Fe-series catalyst, and its consumption is 20-100 kilogram/ton coal.
5, fluidization hydrogenation liquefaction method for coal according to claim 1 is characterized in that: described promotor is a hydrogen sulfide, and its consumption is 0.5-10 kilogram/ton coal.
6, fluidization hydrogenation liquefaction method for coal according to claim 1 is characterized in that: described fluidized-bed reactor reaction conditions is: working pressure 0.05-6.0MPa, service temperature 380-560 ℃, gas-solid ratio 1.0-20: 1 (v/v).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101510863A CN100441663C (en) | 2006-12-01 | 2006-12-01 | Fluidization hydrogenation liquefaction method for coal |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101510863A CN100441663C (en) | 2006-12-01 | 2006-12-01 | Fluidization hydrogenation liquefaction method for coal |
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| Publication Number | Publication Date |
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| CN1970690A true CN1970690A (en) | 2007-05-30 |
| CN100441663C CN100441663C (en) | 2008-12-10 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191075A (en) * | 2010-03-17 | 2011-09-21 | 肇庆市顺鑫煤化工科技有限公司 | Lignite solubilizing and catalytic liquefaction method in non-hydrogen atmosphere |
| CN102391886A (en) * | 2011-09-27 | 2012-03-28 | 长安大学 | Dry distillation and liquefying method for coal |
| CN109355098A (en) * | 2018-09-19 | 2019-02-19 | 北京三聚环保新材料股份有限公司 | A kind of low grade oils multi-stage conversion process |
| CN111234855A (en) * | 2020-01-17 | 2020-06-05 | 广东润丰实业有限公司 | Method for replacing petroleum crude oil by clean coal self-hydrogenation liquefied coalification oil |
| CN111704935A (en) * | 2020-08-03 | 2020-09-25 | 陕西延长石油（集团）有限责任公司 | Low-rank coal hydrogenation-pyrolysis-gasification coupling integrated poly-generation process method |
| US11492563B2 (en) | 2018-04-28 | 2022-11-08 | Beijing Sanju Environmental Protection & New Materials Co., Ltd | Conversion process for an inferior oil |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4235699A (en) * | 1979-03-05 | 1980-11-25 | Allied Chemical Corporation | Solubilization of coal with hydrogen sulfide and carbon monoxide |
| JP2001164263A (en) * | 1999-12-08 | 2001-06-19 | Kobe Steel Ltd | Method for liquefying coal |
| CN1257252C (en) * | 2004-07-30 | 2006-05-24 | 神华集团有限责任公司 | Method for directly liquefying coal |
-
2006
- 2006-12-01 CN CNB2006101510863A patent/CN100441663C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191075A (en) * | 2010-03-17 | 2011-09-21 | 肇庆市顺鑫煤化工科技有限公司 | Lignite solubilizing and catalytic liquefaction method in non-hydrogen atmosphere |
| CN102391886A (en) * | 2011-09-27 | 2012-03-28 | 长安大学 | Dry distillation and liquefying method for coal |
| US11492563B2 (en) | 2018-04-28 | 2022-11-08 | Beijing Sanju Environmental Protection & New Materials Co., Ltd | Conversion process for an inferior oil |
| CN109355098A (en) * | 2018-09-19 | 2019-02-19 | 北京三聚环保新材料股份有限公司 | A kind of low grade oils multi-stage conversion process |
| CN111234855A (en) * | 2020-01-17 | 2020-06-05 | 广东润丰实业有限公司 | Method for replacing petroleum crude oil by clean coal self-hydrogenation liquefied coalification oil |
| CN111704935A (en) * | 2020-08-03 | 2020-09-25 | 陕西延长石油（集团）有限责任公司 | Low-rank coal hydrogenation-pyrolysis-gasification coupling integrated poly-generation process method |
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| Publication number | Publication date |
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| CN100441663C (en) | 2008-12-10 |
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Owner name: SHAANXI COAL AND CHEMICAL INDUSTRY GROUP SHENMU TI Free format text: FORMER OWNER: WANG SHOUFENG Effective date: 20140922 Free format text: FORMER OWNER: LV ZISHENG LI XIUHUI Effective date: 20140922 |
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Effective date of registration: 20140922 Address after: 719319 Shenmu Tianyuan Chemical Industry Co., Ltd., Shaanxi coal chemical industry group, Shenmu Industrial Zone, Shenmu City, Shaanxi, Yulin Patentee after: Shaanxi Coal and Chemical Industry Group Shenmu Tianyuan Chemical Industry Co., Ltd. Address before: 719319, Shenmu county, Shaanxi City, Yulin Province Kam Industrial Park Shenmu Kam Tianyuan Chemical Co., Ltd. Patentee before: Wang Shoufeng Patentee before: Lv Zisheng Patentee before: Li Xiuhui |