CN102030606A - Processing method for removing pyridine compound from coal coking crude benzene by fixed bed supplemental refining and hydrorefining processing - Google Patents
Processing method for removing pyridine compound from coal coking crude benzene by fixed bed supplemental refining and hydrorefining processing Download PDFInfo
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Abstract
The invention provides a method for processing coal coking crude benzene serving as a raw material by fixed bed supplemental refining and hydrorefining. The method comprises the following steps of: removing heavy benzol from coal coking crude benzene serving as the raw material; exchanging heat in a heat exchanger to be normal temperature of 78 DEG C; performing a hybrid reaction on the coal coking crude benzene and a pyridine compound removing agent by using a static mixer; settling and separating dregs by using a settling tank; discharging the settled dregs from the bottom of the settling tank; allowing the refined crude benzene to enter an electric settling tank; discharging the settled dregs from the bottom of the settling tank; washing the crude benzene on the upper layer with water or/and removing residual components of the coking crude benzene in the process of removing the pyridine compound by using a fixed bed; performing heat exchange on the refined crude benzene by using a heat exchanger; allowing the refined crude benzene to enter a hydrogenation device to perform hydrorefining treatment; and allowing the obtained liquid benzene to enter a benzene separating tower to obtain products such as refined benzene, methylbenzene and dimethylbenzene. By the method, the residual components of the coking crude benzene in the process of removing the pyridine compound are removed and the influence on hydrogenation is avoided.
Description
Technical field
The invention belongs to chemical technology field, is the technology of feedstock production refining benzene with the coal tar crude benzol particularly.
Background technology
The byproduct coking crude benzene that produces in the coal tar process is an important industrial chemicals of producing benzene (B), toluene (T), dimethylbenzene (X).Contain a large amount of unsaturated hydrocarbons and sulfur-bearing nitrogenous compound in the coal coking benzene, as straight-chain paraffin mercaptan, aromatic base mercaptan, thioether, thiophene, dibenzothiophene, benzo-thiophene, pyridine, picoline and lutidine etc.BTX is during as the basic Organic Chemicals of one-level, and these impurity need remove, thereby reach the purpose of purification.
At present, the method for crude benzene refining has three kinds: sulfuric acid method for making, extraction fractional distillation and hydrofining.The sulfuric acid treatment method is simple to operate, but has that degree of purification is low, the benzene yield is low and problem such as acid sludge is difficult, and environmental issue is outstanding, is eliminated gradually; Extraction fractional distillation exist energy consumption height, quality product be difficult to control, to problem such as the low coking crude benzene of thiophene content is inapplicable; The quality product height that hydrofining obtains, the aromatic hydrocarbons loss is little, becomes the main flow trend of crude benzene refining gradually.
The technology that is used for the coking crude benzene shortening abroad mainly contains the Uhde low temperature gas phase hydrogenation method of the Axens low temperature of the U.S. (320 ℃～380 ℃) gas-liquid two-phase hydrogenation method, Germany and high temperature (600 ℃～630 ℃) the high pressure vapor hydrogenation Litol method of Japan.The refining level of external crude benzole hydrogenation is higher, mainly be the quality that relies on its catalyzer, and high-temperature and high-pressure hydrogenation is very high to the material and the specification of quality of device, manufacture difficulty is very big with investment, operation running risk is relatively large, bears all being difficult on the general business economic.
Chinese patent CN1948244A discloses a kind of technology by coking benzene hydrogenation desulfurization denitrogenation producing refined benzene, mainly comprises coking benzene pre-treatment rectification step, three grades of desulfurized steps, purification step etc.Chinese patent CN101486623A discloses a kind of hydrofinishing method for crude benzol, the coking crude benzene raw material is after pre-treatment, after taking off heavily, decompression carries out pre-hydrotreating reaction and main hydrogenation reaction, gaseous phase materials after the hydrogenation reaction enters hp flash drum, isolate hydrogen-rich gas, liquid phase enters stabilizer tower and removes low boiling hydrocarbon, enters aromatic extraction unit at last, extracting obtains highly purified triphen, the problem that exists the catalyst for pre-hydrogenation bed pressure drop to raise.Chinese patent CN101519338A discloses a kind of process for hydrofining coking crude benzene, and, dimethylbenzene distillation unit refining by raw material pre-separation, hydrofining, fore-distillation, extractive distillation, aromatic hydrocarbons formed; This invention can reduce the aromatic hydrocarbons loss to a certain extent, and quality product can reach the quality of petroleum benzene.But no matter be external hydrogen addition technology or domestic hydrogen addition technology, all do not have after taking off heavily, separately the pyridines material to be removed, and pyridine compounds and their content height in the coal tar crude benzol in the conventional hydrogenation unit charging, these compounds are basic nitrogen compounds, severe inhibition the thiophenes hydrodesulfurization reaction, be the maximum inhibition of hydrodesulfurization reaction.They are vied each other by the hydrogenation approach in catalyst active center, and denitrification reaction is slower than desulphurization reaction, and nitride is trapped in the time ratio sulfide in active centre and will grows, and therefore can reduce desulfurization rate, and shorten the work-ing life of hydrogenation catalyst greatly.This shows, the pyridine compounds and their that pre-treatment removes in the hydrogenating materials is very necessary, and denitrfying agent that provides with ZL94115190.5 or other acidic components denitrfying agent and denitrfying agent have bigger solubleness with pyridine compounds and their in crude benzol than in oil product, their residual meetings in crude benzol are adsorbed on catalyst surface, have reduced the surfactivity of expensive hydrogenation catalyst.
The objective of the invention is to solve the residual problem of pyridine compounds and their component of taking off, reduce influence, preparation sulphur, the carbonization benezene that nitrogen content is low, unsaturated hydrocarbons content is low, quality is high following process.Provide a kind of coal tar crude benzol to take off pyridine compounds and their post-refining-hydrorefined working method.
Summary of the invention
The invention provides a kind of is raw material with the coal tar crude benzol, by taking off the refining combination process that carries out hydrotreatment again of pyridine compounds and their, it is characterized in that coal tar crude benzol (1) is removed heavy benzol in taking off heavies column (A), take off after heavy crude benzol with take off pyridine compounds and their and in static mixer (B), carry out hybrid reaction with agent (2) after, enter electrofining slurry tank (C) or/and the middle sedimentation of natural subsidence jar (D) divides slag, sediment (3) (4) from slurry tank (C) or/and (D) bottom discharge, make with extra care and take off pyridine benzene (5) through interchanger (E) heat exchange, after washing (F) is or/and fixed bed (G) removes the residual component that coking crude benzene exists in taking off the pyridine compounds and their process, enter hydrogenation system (H) at last and carry out the hydrofining processing, with post reaction mixture (6) through the cooling, after the separation, the liquid benzene that obtains enters in the benzaldehyde product separation system (I), obtains product purification benzene, toluene, dimethylbenzene (7).
Taking off pyridine compounds and their among the present invention is the 0.2%-5% of raw material with the adding weight percent of agent (2).Hydrobon catalyst is housed in the hydrogenation system, catalyzer is to be carrier with aluminum oxide, amorphous silicon aluminium or molecular sieve, with Co, Mo and Ni is main active ingredient, and preferred activeconstituents is the catalyzer of Co-Mo series, comprises with the Co-Mo catalyst series being all catalyzer of basic modification; Hydrogenation temperature can be the arbitrary value between 80 ℃～630 ℃, and hydrogen to oil volume ratio is 100: 1～3000: 1, and volume space velocity is 0.1h
-1～15h
-1, the reaction stagnation pressure is 0.5Mpa～21Mpa.
The order of electrofining slurry tank (C) and slurry tank (D) can be exchanged among the present invention, and the electrofining strength of electric field in the electrofining slurry tank (C) is at 0-2000 volt/cm
2Scope.
Filler in the fixed bed that adopts among the present invention (G) is:
A. the oxide compound of solid alkali metal, alkaline-earth metal and oxyhydroxide thereof, as: Na
+, K
+, Ca
+ 2, Mg
+ 2, Al
+ 3, Zn
+ 2, Fe
+ 2, Fe
+ 3, Ba
+ 2, Pb
+ 2Oxide compound and oxyhydroxide etc. thereof.
B. the salt that generates of solid alkali weak acid, as: Na
2CO
3, Na
3PO
4, K
2CO
3Deng.
C. porous mass comprises gac, coke, coal, cinder, carclazyte, diatomite, silica gel, aluminum oxide, molecular sieve, porous organo polysilica compound, ion exchange resin, chitin etc.
D.c adsorbed a or (with) b, or (with) inorganic ammonia, organic amine, acid amides, as: the absorption Monomethylamine, ethamine, azanol, urea, triethylamine, quadrol and diethylenetriamine, aniline, ethylaniline, Ortho Toluidine and xylidine, thanomin (has one, two, trolamine), methylamine (second, third, fourth ... stearylamine), quadrol (third, fourth, penta, hexanediamine etc.), acid amides (first, second, propionic acid amide, methylformamide, methylacetamide, dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.), dimethyl formamide, dimethylethanolamine, N methyldiethanol amine, Yi Bingchunan, aryloxy propanol amine, trolamine, phosphorylethanolamine, benzene oxygen Propanolamine, Phenylethanolamine, tri-isopropanolamine, N-aminoethyl ethanolamine, diethylenetriamine, alkanolamine, alkylene amines, ammoniacal liquor, the sorbent material of phosphorus ammonium phosphoric acid hydrogen ammonia primary ammonium phosphate etc.
E. the filler of fixed bed is a, b, c, a kind of and mixture among the d.
Taking off the pyridine compounds and their unit in the present invention can be also can be after taking off heavy constituent before the coal tar crude benzol takes off heavy constituent.
The pyridine compounds and their that takes off that the present invention adopts can be the denitrfying agent that ZL94115190.5 provides with agent, but is not limited to this denitrfying agent, can be existing denitrfying agent, and they are acid but do not comprise sulfuric acid, or the mixture of acid.The described hydrofining technology of this patent can be existing hydrofining technology, but is not limited to existing hydrofining technology, comprises the improvement of hydrofining technology.Washing (F) is conventional washing; Fixed bed (G) refining with adsorbents and benzaldehyde product separation system (I) are prior art.
Description of drawings
Fig. 1 is the process flow sheet of wax tailings working method of the present invention.Number among the figure:
1 coking crude benzene; 2 denitrification refining agent; 3 sediments; 4 sediments; 5 take off pyridine benzene; Product behind 6 hydrogenation; 7. benzene,toluene,xylene product.
A: take off heavies column; B: static mixer; C, D: electrofining slurry tank or slurry tank; E: interchanger; F: washing; G: fixed bed; H: hydrogenation system; I: benzaldehyde product separation system.
Fig. 2 is the process flow diagram of reference example.Number among the figure:
The I coking crude benzene; Product behind the II hydrogenation; III benzene,toluene,xylene product.
X: take off heavies column Y: hydrofining system; Z: benzaldehyde product separation system.
Embodiment
The present invention implements like this: coking crude benzene 1 through the crude benzol that taking off heavies column (A) and obtain with take off pyridine refining agent 2 and in (B), mix.This takes off pyridine compounds and their can be the denitrfying agent that ZL94115190.5 provides with agent, but is not limited to this denitrfying agent, can be existing denitrfying agent, and they are acid but do not comprise sulfuric acid, or the mixture of acid.Can reduce to 1-20ppm by the basic nitrogen compound that takes off pyridine benzene (5) that takes off after pyridine compounds and their is handled.Taking off pyridine compounds and their is the 0.2%-5% of raw material with the adding weight percent of agent (2); Mixing temperature is normal temperature～78 ℃. mixed crude benzol enters electrofining slurry tank (C) or/and slurry tank (D) carries out settlement separate; Separating tank comes out take off pyridine benzene (5) and enter well heater (E) again and be heated to 200-350 ℃ after, or/and removing coking crude benzene, fixed bed (G) refining with adsorbents taking off the residual component that exists in the pyridine compounds and their process through washing (F), enter hydrogenation system (H) at last and carry out the hydrofining processing, the catalyzer that adopts be existing hydrogen addition technology commonly used be the Co-Mo catalyzer or the improved hydrogenation catalyst of carrier with the molecular sieve, hydrogenation pressure is 0.5Mpa～21Mpa, and air speed is 0.1h
-1～15h
-1, the coking benzene after the hydrofining (6) enters benzaldehyde product separation system (I) can obtain the benzene,toluene,xylene product.
The present invention is described in further detail below in conjunction with embodiment.But this should be interpreted as that the above-mentioned theme of the present invention only limits to following embodiment.
Reference example: referring to Fig. 2, coking crude benzene takes off heavy back crude benzol and directly enters hydrogenation system (Y) taking off heavies column (X), and hydrogenation catalyst is to be the Co-Mo catalyzer of carrier with the molecular sieve, 380 ℃ of hydrogenation temperatures, pressure 3.0Mpa, air speed 2h
-1, hydrogen-oil ratio 550: 1 can obtain qualified product by benzaldehyde product separation system (Z) behind the hydrogenation, and in the product refining benzene that obtains, benzene content is 99.9%, and sulphur content is 0.93ppm, and nitrogen content is 5ppm.
Embodiment 1: referring to Fig. 1, coking crude benzene takes off denitrfying agent that the crude benzol after heavy provides with 2% ZL94115190.5 and takes off pyridine as taking off pyridine agent (down with), pyridine content is reduced to 12mg/kg from 3684 μ g/g, acid number is 0.053mgKOH/g, use the granular carclazyte post-refining, acid number is reduced to 0.00012mgKOH/g, the later crude benzol of post-refining carries out hydrogenation, hydrogenation catalyst is to be the Co-Mo catalyzer (down together) of carrier with the molecular sieve, the processing condition of hydrogenation: 380 ℃ of temperature, pressure 3.0Mpa, air speed 2h
-1, hydrogen-oil ratio 550: 1, refining crude benzol enters the benzaldehyde product separation system and obtains benzene,toluene,xylene, and benzene content is 99.93%, and sulphur content is 0.49ppm, and nitrogen content is 1ppm, hydro-refining unit operation 4 days, pressure drop does not have increase.
Embodiment 2: the crude benzol that takes off after heavy takes off pyridine with the pyridine agent of taking off that 2% ZL94115190.5 provides, pyridine content is reduced to 12mg/kg from 3684 μ g/g, acid number is 0.053mgKOH/g, with the gac post-refining that has adsorbed 10%NaOH, acid number is reduced to 0.000023mgKOH/g, and the later crude benzol of post-refining carries out hydrogenation, hydrogenation catalyst is to be the Co-Mo catalyzer of carrier with the molecular sieve, 380 ℃ of hydrogenation temperatures, pressure 3.0Mpa, air speed 2.8h
-1, hydrogen-oil ratio 550: 1, in the product refining benzene that obtains, benzene content is 99.9%, and sulphur content is 0.86ppm, and nitrogen content is 2.6ppm, hydro-refining unit operation 4 days, pressure drop does not have increase.
Embodiment 3: the crude benzol that takes off after heavy takes off pyridine with the pyridine agent of taking off that 2% ZL94115190.5 provides, pyridine content is reduced to 12mg/kg from 3684 μ g/g, acid number is 0.053mgKOH/g, with the chitin post-refining that has adsorbed trolamine, acid number is reduced to 0.00013mgKOH/g, and the later crude benzol of post-refining carries out hydrogenation, hydrogenation catalyst is to be the Co-Mo catalyzer of carrier with the molecular sieve, 369.2 ℃ of hydrogenation temperatures, pressure 3.0Mpa, air speed 2h
-1, hydrogen-oil ratio 550: 1, in the product refining benzene that obtains, benzene content is 99.9%, and sulphur content is 0.91ppm, and nitrogen content is 2.3ppm, hydro-refining unit operation 4 days, pressure drop does not have increase.
Embodiment 4: the crude benzol that takes off after heavy takes off pyridine with the pyridine agent of taking off that 2% ZL94115190.5 provides, and pyridine content is reduced to 12mg/kg from 3684 μ g/g, and acid number is 0.053mgKOH/g, with 1% solid Ca (OH)
2Post-refining, acid number is reduced to 0.00056mgKOH/g, and the later crude benzol of post-refining carries out hydrogenation, hydrogenation catalyst is to be the Co-Mo catalyzer of carrier with the molecular sieve, 380 ℃ of hydrogenation temperatures, pressure 2.7Mpa, air speed 2h-1, hydrogen-oil ratio 550: 1, in the product refining benzene that obtains, benzene content is 99.9%, sulphur content is 0.89ppm, nitrogen content is 2.1ppm, hydro-refining unit operation 4 days, and pressure drop does not have increase.
Among the present invention, if no special instructions, all percentage ratios are weight percentage.
Claims (9)
1. one kind is raw material with the coal tar crude benzol, by taking off the refining combination process that carries out hydrotreatment again of pyridine compounds and their, after it is characterized in that coal tar crude benzol (1) removed heavy benzol in taking off heavies column (A), with take off pyridine compounds and their and in static mixer (B), carry out hybrid reaction with agent (2), enter electrofining slurry tank (C) or/and the middle sedimentation of natural subsidence jar (D) divides slag, sediment (3) (4) from slurry tank (C) or/and (D) bottom discharge, refining take off pyridine benzene (5) through interchanger (E) heat exchange to 200～350 ℃ after washing (F) is being taken off the residual component that exists in the pyridine compounds and their process or/and fixed bed (G) removes coking crude benzene, enter hydrogenation system (H) at last and carry out the hydrofining processing, with post reaction mixture (6) through the cooling, after the separation, the liquid benzene that obtains enters in the benzaldehyde product separation system (I), obtains product purification benzene, toluene, dimethylbenzene (7).
2. method according to claim 1, it is characterized in that taking off pyridine compounds and their is the 0.2%-5% of raw material with the adding weight percent of agent (2).
3. method according to claim 1, its feature also are in hydrogenation system (H) hydrogenation unit Hydrobon catalyst to be housed, and catalyzer is to be carrier with aluminum oxide, amorphous silicon aluminium or molecular sieve, is main active ingredient with Co, Mo and Ni.
4. method according to claim 3, it is characterized in that in hydrogenation system (H) hydrogenation unit Hydrobon catalyst being housed, catalyzer is to be carrier with aluminum oxide, amorphous silicon aluminium or molecular sieve, activeconstituents is the catalyzer of Co-Mo series, comprises with the Co-Mo catalyst series being all catalyzer of basic modification.
5. method according to claim 3, its feature are that also hydrogenation system (H) hydrogenation temperature can be the arbitrary value between 80 ℃～630 ℃, and hydrogen to oil volume ratio is 100: 1～3000: 1, and volume space velocity is 0.1h
-1～15h
-1, the reaction stagnation pressure is 0.5Mpa～21Mpa.
6. method according to claim 1, its feature also is: the order of electrofining slurry tank (C) and slurry tank (D) can be exchanged.
7. method according to claim 1 is characterized in that: the electrofining strength of electric field in the electrofining slurry tank (C) is at 0-2000 volt/cm
2Scope.
8. method according to claim 1, its feature also is: the filler in the fixed bed that is adopted (G) is
A. the oxide compound of solid alkali metal, alkaline-earth metal and oxyhydroxide thereof are selected from: Na
+, K
+, Ca
+ 2, Mg
+ 2, Al
+ 3, Zn
+ 2, Fe
+ 2, Fe
+ 3, Ba
+ 2, Pb
+ 2Oxide compound and oxyhydroxide thereof;
B. the salt of solid alkali weak acid generation is selected from: Na
2CO
3, Na
3PO
4, K
2CO
3
C. porous mass comprises gac, coke, coal, cinder, carclazyte, diatomite, silica gel, aluminum oxide, molecular sieve, porous organo polysilica compound, ion exchange resin, chitin;
D.c adsorbed a or (with) b, or (with) inorganic ammonia, organic amine, acid amides, as: the absorption Monomethylamine, ethamine, azanol, urea, triethylamine, quadrol and diethylenetriamine, aniline, ethylaniline, Ortho Toluidine and xylidine, thanomin (has one, two, trolamine), methylamine (second, third, fourth ... stearylamine), quadrol (third, fourth, penta, hexanediamine etc.), acid amides (first, second, propionic acid amide, methylformamide, methylacetamide, dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.), dimethyl formamide, dimethylethanolamine, N methyldiethanol amine, Yi Bingchunan, aryloxy propanol amine, trolamine, phosphorylethanolamine, benzene oxygen Propanolamine, Phenylethanolamine, tri-isopropanolamine, N-aminoethyl ethanolamine, diethylenetriamine, alkanolamine, alkylene amines, ammoniacal liquor, the sorbent material of phosphorus ammonium phosphoric acid hydrogen ammonia primary ammonium phosphate;
E. the filler of fixed bed is a, b, c, a kind of and mixture among the d.
9. method according to claim 1, its feature also is: taking off the pyridine compounds and their unit can be also can be after taking off heavy constituent before the coal tar crude benzol takes off heavy constituent.
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775326A (en) * | 2012-08-07 | 2012-11-14 | 中国石油化工股份有限公司 | Method for reducing inactivation of hydroxylamine inorganic liquid |
| CN102850175A (en) * | 2012-09-29 | 2013-01-02 | 北京旭阳化工技术研究院有限公司 | Method for purifying coked benzene |
| CN103044318A (en) * | 2013-01-25 | 2013-04-17 | 山东元利科技股份有限公司 | Method for extracting pyridine from coked crude benzene |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160331B (en) * | 2013-03-29 | 2014-12-10 | 陕西煤业化工技术研究院有限责任公司 | System and process for preparing PTA/PET (Pure Terephthalic Acid/Polyethylene Terephthalate) based on pyrolysis and gasification devices |
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|---|---|---|---|---|
| EP1564199A1 (en) * | 2002-10-24 | 2005-08-17 | Aleksandr Olegovich Naumenko | Method for producing benzene from benzene and /or alkylbenzene-containing mixtures having a high content of sulphur-containing substances |
| CN101486623A (en) * | 2008-01-18 | 2009-07-22 | 沈和平 | Hydrofinishing method for crude benzol |
| CN101519338A (en) * | 2009-02-25 | 2009-09-02 | 中国石油集团工程设计有限责任公司抚顺分公司 | Process for hydrofining coking crude benzene |
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2010
- 2010-12-06 CN CN 201010574467 patent/CN102030606B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1564199A1 (en) * | 2002-10-24 | 2005-08-17 | Aleksandr Olegovich Naumenko | Method for producing benzene from benzene and /or alkylbenzene-containing mixtures having a high content of sulphur-containing substances |
| CN101486623A (en) * | 2008-01-18 | 2009-07-22 | 沈和平 | Hydrofinishing method for crude benzol |
| CN101519338A (en) * | 2009-02-25 | 2009-09-02 | 中国石油集团工程设计有限责任公司抚顺分公司 | Process for hydrofining coking crude benzene |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775326A (en) * | 2012-08-07 | 2012-11-14 | 中国石油化工股份有限公司 | Method for reducing inactivation of hydroxylamine inorganic liquid |
| CN102775326B (en) * | 2012-08-07 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of method reducing inactivation of hydroxylamine inorganic liquid |
| CN102850175A (en) * | 2012-09-29 | 2013-01-02 | 北京旭阳化工技术研究院有限公司 | Method for purifying coked benzene |
| CN102850175B (en) * | 2012-09-29 | 2015-06-03 | 北京旭阳化工技术研究院有限公司 | Method for purifying coked benzene |
| CN103044318A (en) * | 2013-01-25 | 2013-04-17 | 山东元利科技股份有限公司 | Method for extracting pyridine from coked crude benzene |
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Address after: 668 No. 435001 Huangshi city of Hubei province xisaishanqu Huangshi Avenue Applicant after: Hubei ZhenHua Chemical Co., Ltd. Applicant after: Huangshi Taihua Industry Science & Technology Development Co., Ltd. Applicant after: Wuhan Institute of Technology Address before: 435001 Huangshi city of Hubei province xisaishanqu village of Liangshan Applicant before: Huangshi Zhenhua Chemical Industry Co., Ltd. Applicant before: Huangshi Taihua Industry Science & Technology Development Co., Ltd. Applicant before: Wuhan Institute of Technology |
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Free format text: CORRECT: APPLICANT; FROM: HUANGSHI ZHENHUA CHEMICAL INDUSTRY CO., LTD. TO: HUBEI ZHENHUA CHEMICAL CO., LTD. |
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