CN101921397A - Halogenated silanes and reaction medium mixed reactor and method - Google Patents
Halogenated silanes and reaction medium mixed reactor and method Download PDFInfo
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- CN101921397A CN101921397A CN2010102612771A CN201010261277A CN101921397A CN 101921397 A CN101921397 A CN 101921397A CN 2010102612771 A CN2010102612771 A CN 2010102612771A CN 201010261277 A CN201010261277 A CN 201010261277A CN 101921397 A CN101921397 A CN 101921397A
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- halogenated silanes
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Abstract
The invention discloses a kind of halogenated silanes that can make fully contacts with reaction medium, promote complete reaction, thereby improve halogenated silanes and the reaction medium mixed reactor and the method for reaction product quality, in this reaction unit, halogenated silanes mixes in halogenated silanes loop ingress with reaction medium, the import of described halogenated silanes loop is arranged in the connecting tube between reaction medium supplying opening and the forced circulation device, or be arranged on the ingress of forced circulation device, between described halogenated silanes supplying opening and the import of halogenated silanes loop, also be provided with diverting device.In this reaction method, the halogenated silanes structural formula is: R
ySiX
4-y, wherein: R is C
nH
m, n is 〉=0 integer; M is 〉=1 integer, and y=1,2 or 3, X are halogen atom; Reaction medium is water, aqueous hydrochloric acid etc.; Halogenated silanes is after diverting device disperses, and in the turbulent region and the reaction medium hybrid reaction of reaction medium, diverting device adopts liquid phase distributor or shower nozzle etc., uses when being particularly suitable for the halogenated silanes hydrolysis reaction.
Description
Technical field
The feed distribution and the mixed structure that the present invention relates to a kind of pipe reaction device improve, and this pipe reaction device belongs to two kinds of liquid phase materials of a kind of thorough mixing and realizes the reactor and the hybrid reaction method thereof of its continuously feeding.
Background technology
At present, the hydrolysis process of domestic dimethyldichlorosilane(DMCS) generally adopts azeotropic hydrochloric acid continuous hydrolysis process, its technology is: join in proportion in the loop reaction mixed reactor of being made up of line mixer, forced circulation device, the interchanger that cold is provided and connecting tube with dimethyldichlorosilane(DMCS) and as reaction medium " the HCl massfraction is 18%～22% azeotropic hydrochloric acid ", hydrolysate passes through physical layering, upper oil phase is through neutralization deacidification, washing desalination or remove alkali, promptly obtains the finished product hydrolyzate.
Hydrochloric acid provides the said hydrolyzed reaction required water, and dimethyldichlorosilane(DMCS) as long as contact with water hydrolysis reaction just takes place.The hydrolysis reaction that dimethyldichlorosilane(DMCS) is mentioned in the front is extremely rapid, to such an extent as to two just occurred reaction when contacting in line mixer.In line mixer, there be the in shortage of water, thereby cause the dimethyldichlorosilane(DMCS) hydrolysis incomplete.In the polysiloxane that hydrolysis obtains, there is a spot of end group chlorine, this a part of end group chlorine has caused the difficulty of subsequent disposal, its reason is that the activity of the Cl terminal group on the long linear polysiloxane is lower, being difficult to remove extremely by neutralization and limited amount washing, desired chlorine residual volume is the content that has neither part nor lot in the chlorine of hydrolysis reaction in the hydrolyzate, and the chlorine remnants that are not effectively addressed will cause dimethyldichlorosilane(DMCS) hydrolysate polysiloxane generation polycondensation, and the viscosity skew takes place.Therefore, there is the deficiency that hydrolysis is incomplete, product chlorine residual volume is bigger in existing mixed reactor.
Existing halogenated silanes and reaction medium mixed reactor mainly comprise by forced circulation device, the loop that interchanger and connecting tube are formed, described loop is provided with the halogenated silanes supplying opening, reaction medium supplying opening and loop outlet, by the halogenated silanes supplying opening, the reactant that the reaction medium supplying opening enters circulates by the direction of " forced circulation device-interchanger-loop outlet " in loop, halogenated silanes mixes in halogenated silanes loop ingress with reaction medium, loop exports on the connecting tube that is arranged between reaction medium supplying opening and the interchanger, interchanger is used for control reaction temperature, under the forced circulation device effect, the reactant and the resultant that enter system flow in order, and are flowed out by the loop outlet.
In existing halogenated silanes and the reaction medium mixed reactor, halogenated silanes has plenty of and directly enters in the loop, have plenty of before entering system, utilize static mixer with halogenated silanes with enter loop after reaction medium mixes, but in known technology for hydrolyzing, mainly be to realize that by aforesaid line mixer liquid liquid biphase mixes and reaction, that is: with halogenated silanes with enter in the loop after reaction medium mixes by line mixer, it is the halogenated silanes supplying opening, the reaction medium supplying opening all is arranged on the line mixer, the mixing point of halogenated silanes and reaction medium, or be referred to as " import of halogenated silanes loop ", also be at the line mixer place, its defective is exactly that hydrolysis is incomplete, product chlorine residual volume is bigger.
The connecting tube that uses in the mixed reactor is generally acidproof pipeline.
Summary of the invention
In order to overcome the deficiency that existing mixed reactor halogenated silanes hydrolysis is incomplete, product chlorine residual volume is bigger, technical problem to be solved by this invention provides a kind of halogenated silanes that makes and fully contacts with reaction medium, promote complete hydrolysis, thereby improve halogenated silanes and the reaction medium mixed reactor and the method for hydrolyzate quality.
The technical solution adopted for the present invention to solve the technical problems is: halogenated silanes and reaction medium mixed reactor, comprise the loop that connects to form through connecting tube by the import of forced circulation device and outlet, described loop is provided with the halogenated silanes supplying opening, reaction medium supplying opening and loop outlet, the loop outlet is after the outlet of forced circulation device, the reaction medium supplying opening is arranged on before the import of forced circulation device, halogenated silanes mixes in halogenated silanes loop ingress with reaction medium, the import of described halogenated silanes loop is arranged on the connecting tube between reaction medium supplying opening and the forced circulation device or the ingress of forced circulation device, also is provided with diverting device between described halogenated silanes supplying opening and the import of halogenated silanes loop.
Described forced circulation device is a pump, and the import of described halogenated silanes loop is arranged in its pump chamber.
Described diverting device is a liquid phase distributor.
Described diverting device is a shower nozzle.
Be provided with interchanger in the described loop, described interchanger is arranged between the outlet and loop outlet of forced circulation device.
Be provided with line mixer between the import of described forced circulation device and the loop outlet, the reaction medium supplying opening of loop is arranged on the line mixer.
The present invention also provides a kind of reaction method that utilizes halogenated silanes of the present invention and reaction medium mixed reactor, reaction medium enters loop by the reaction medium supplying opening, described loop is connected to form through connecting tube with outlet by the import of forced circulation device, and under the forced circulation device effect, circulate, halogenated silanes is behind diverting device, in the connecting tube between reaction medium supplying opening and forced circulation device, or give birth to reaction in the import of forced circulation device and reaction medium hybrid concurrency.
Described halogenated silanes structural formula is: R
ySiX
4-y,
Wherein: R is C
nH
m, n is 〉=0 integer; M is 〉=1 integer, and y=1,2 or 3, X are halogen atom;
Described reaction medium is water, aqueous hydrochloric acid, methanol aqueous solution, aqueous sodium carbonate, sodium chloride aqueous solution or aqueous sodium hydroxide solution.
The invention has the beneficial effects as follows: by optimizing the layout of halogenated silanes supplying opening on the mixed reactor loop, reaction medium supplying opening and loop outlet, change the feed entrance point and the feeding manner of halogenated silanes in the hydrolytic process, halogenated silanes is fully contacted with reaction medium, promote complete hydrolysis, when reducing hydrolysate viscosity, reduce the halogen residual volume of hydrolysate, saved production cost.
Description of drawings
Fig. 1 is the synoptic diagram of existing mixed reactor.
Fig. 2 is the synoptic diagram of mixed reactor of the present invention.
Fig. 3 is the synoptic diagram of another embodiment of mixed reactor of the present invention.
Fig. 4 is the synoptic diagram of the another embodiment of mixed reactor of the present invention.
Fig. 5 is the synoptic diagram of a position of halogenated silanes loop import.
Fig. 6 is the synoptic diagram of another position of halogenated silanes loop import.
Be labeled as 1-line mixer, 2-forced circulation device, 3-interchanger, 4-diverting device among the figure, the 5-connecting tube, the import of 6-halogenated silanes loop, 7-pump chamber, 11-halogenated silanes supplying opening, 12-reaction medium supplying opening, the outlet of 13-loop, 20-import, 21-outlet.
Embodiment
The present invention is further described below in conjunction with accompanying drawing, embodiment and experiment.
Figure 1 shows that existing mixed reactor, it comprises by line mixer 1, forced circulation device 2, the interchanger 3 of cold is provided and connects the loop that connecting tube 5 is therebetween formed, line mixer 1 is provided with halogenated silanes supplying opening 11 and reaction medium supplying opening 12, enter and hydrolysis reaction takes place immediately and generate hydrolyzate after the halogenated silanes of line mixer 1 and reaction medium mix, under forced circulation device 2 effect at the loop internal recycle, and heating under interchanger 3 effect, hydrolyzate goes to next chemical unit and handles through being arranged on loop outlet 13 on the connecting tube 5 between line mixer 1 and the interchanger 3.
As Fig. 2, Fig. 3, Fig. 4, Fig. 5 and shown in Figure 6, halogenated silanes of the present invention and reaction medium mixed reactor comprise the loop that is connected to form through connecting tube 5 by the import 20 of forced circulation device 2 and outlet 21, described loop is provided with halogenated silanes supplying opening 11, reaction medium supplying opening 12 and loop outlet 13, loop outlet 13 is after the outlet 21 of forced circulation device 2, reaction medium supplying opening 12 is arranged on before the import 20 of forced circulation device 2, halogenated silanes mixes at halogenated silanes loop import 6 places with reaction medium, described halogenated silanes loop import 6 is arranged on the connecting tube 5 between reaction medium supplying opening 12 and the forced circulation device 2 or import 20 places of forced circulation device 2, also is provided with diverting device 4 between described halogenated silanes supplying opening 11 and halogenated silanes loop import 6.By changing the feed entrance point and the feeding manner of halogenated silanes in the hydrolytic process, enter the turbulent region that the pump circulation because of reaction medium forms behind the utilization diverting device 4 refinement halogenated silanes drops again, the mixing fully that has promoted halogenated silanes and reaction medium with fully contact, the mass transfer speed of hydrolytic process is fast, disperse and good mixing effect, the acceleration that is exceedingly fast the hydrolysis process, in the extremely short residence time, hydrolysate viscosity is lower, reduces the halogen residual volume of hydrolysate simultaneously.
During better scheme is, described forced circulation device 2 is a pump, described loop import 6 is arranged in its pump chamber 7, halogenated silanes after promptly distributing directly enters in the pump chamber 7, then halogenated silanes is after preliminary the dispersion, in pump chamber 7, carry out initial reaction with reaction medium, mixing two-phase that is exceedingly fast and broken two-phase small droplets, thus reach the effect of mixing and improving reaction.
Described diverting device 4 can adopt the chemical industry liquid phase distributor of known conventional, as traverse baffle etc.
Described diverting device 4 is preferably shower nozzle, and dispersion effect is better.
Usually, should be provided with interchanger 3 in described loop, described interchanger 3 is arranged between the outlet 21 and loop outlet 13 of forced circulation device 2, so that control reaction temperature.
If improve on former line mixer formula reaction unit basis, described line mixer 1 operated by rotary motion is between the import 20 and loop outlet 13 of forced circulation device 2, and the reaction medium supplying opening 12 that still can keep loop is on line mixer 1.
Utilize the halogenated silanes and the reaction medium hybrid reaction method of halogenated silanes of the present invention and reaction medium mixed reactor, reaction medium enters loop by reaction medium supplying opening 12, described loop is connected to form through connecting tube 5 by the import 20 of forced circulation device 2 and outlet 21, and under forced circulation device 2 effects, circulate, halogenated silanes is behind diverting device 4, in the connecting tube 5 between reaction medium supplying opening 12 and forced circulation device 2, or give birth to reaction with the reaction medium hybrid concurrency in the import 20 of forced circulation device 2.
Halogenated silanes of the present invention and reaction medium mixed reactor halogenated silanes applicatory can be dimethyldichlorosilane(DMCS), monomethyl dichlorosilane, trimethylchlorosilane, diphenyl dichlorosilane etc., and reaction medium can be aqueous hydrochloric acid, methanol aqueous solution, aqueous sodium carbonate, sodium chloride aqueous solution, aqueous sodium hydroxide solution of water, different concns etc.
The halogenated silanes structural formula is: R
ySiX
4-y,
Wherein: R is C
nH
m, n is 〉=0 integer; M is 〉=1 integer, and y=1,2 or 3, X are halogen atom;
When reaction medium is water, aqueous hydrochloric acid, methanol aqueous solution, aqueous sodium carbonate, sodium chloride aqueous solution or aqueous sodium hydroxide solution, all can use halogenated silanes of the present invention and reaction medium mixed reactor.
In the hybrid reaction method of the present invention, the control of reaction raw materials ratio and temperature of reaction is with to have method now identical, it is to utilize diverting device refinement drop earlier before halogenated silanes mixes with the key distinction of existing method, and change has taken place the mixing point of halogenated silanes and reaction medium.
Embodiment one:
As Fig. 2 and shown in Figure 5, halogenated silanes of the present invention and reaction medium mixed reactor comprise the loop that is connected to form through connecting tube 5 by the import 20 of forced circulation device 2 and outlet 21, described loop is provided with halogenated silanes supplying opening 11, reaction medium supplying opening 12 and loop outlet 13, loop outlet 13 is after the outlet 21 of forced circulation device 2, reaction medium supplying opening 12 is arranged on before the import 20 of forced circulation device 2, halogenated silanes mixes at halogenated silanes loop import 6 places with reaction medium, halogenated silanes loop import 6 is arranged on the connecting tube 5 between the import 20 of reaction medium supplying opening 12 and forced circulation device 2, also be provided with diverting device 4 between described halogenated silanes supplying opening 11 and halogenated silanes loop import 6, resultant is through forced circulation device 2, interchanger 3, loop outlet 13 is flowed out.
Embodiment two:
As shown in Figure 3, halogenated silanes of the present invention and reaction medium mixed reactor comprise the loop that is connected to form through connecting tube 5 by the import 20 of forced circulation device 2 and outlet 21, described loop is provided with halogenated silanes supplying opening 11, reaction medium supplying opening 12 and loop outlet 13, loop outlet 13 is after the outlet 21 of forced circulation device 2, reaction medium supplying opening 12 is arranged on before the import 20 of forced circulation device 2, halogenated silanes mixes at halogenated silanes loop import 6 places with reaction medium, halogenated silanes loop import 6 is arranged in the pump chamber 7 as the pump of forced circulation device 2, also is provided with diverting device 4 between described halogenated silanes supplying opening 11 and halogenated silanes loop import 6.
Embodiment three:
Present embodiment is formed by the existing mixed reactor transformation that is provided with line mixer 4.As Fig. 4 and shown in Figure 6, halogenated silanes of the present invention and reaction medium mixed reactor comprise the loop of being made up of line mixer 4, forced circulation device 2, interchanger 3 and connecting tube 5, reaction medium supplying opening 12 still is arranged on the line mixer 4, and halogenated silanes arrives halogenated silanes loop import 6 places that are arranged on the forced circulation device 2 and mixes with reaction medium through halogenated silanes supplying opening 11, diverting device 4.
Experiment one:
Do the contrast experiment with the former mixed reactor of hydrolysis method process using of dimethyldichlorosilane(DMCS) and azeotropic hydrochloric acid and the mixed reactor of the embodiment of the invention one, reaction medium is an azeotropic hydrochloric acid.
Adopt former mixed reactor, respectively with 2m
3/ h and 8m
3The flow of/h enters into the loop system of being made up of line mixer 1, forced circulation device 2, the interchanger 3 that cold is provided and connecting tube 5 continuously with dimethyldichlorosilane(DMCS) and azeotropic hydrochloric acid, and hydrolysis temperature is controlled at 0 ℃～40 ℃.Hydrolysate is by physical layering, and upper oil phase is through neutralization deacidification, washing desalination or remove alkali, obtains the finished product hydrolyzate.
Adopt the mixed reactor of the embodiment of the invention one, with 2m
3The dimethyldichlorosilane(DMCS) of/h enters into the connecting tube 5 between forced circulation device 2 and the line mixer 1 after distributing as the shower nozzle of diverting device 4, with azeotropic hydrochloric acid with 8m
3/ h flow enters into line mixer 1, and hydrolysis temperature is controlled at 0 ℃～40 ℃.Hydrolysate is by physical layering, and upper oil phase is through neutralization deacidification, washing desalination or remove alkali, obtains the finished product hydrolyzate.
Two kinds of finished product hydrolyzate analytical results such as following tables one that device produces.
Table one
| Reaction unit | Acid content (ppm) | Viscosity (mPas) |
| Former mixed reactor | 316 | 12.44 |
| Mixed reactor of the present invention | 7.02 | 6.35 |
When adopting mixed reactor of the present invention, the hydrolysate acid content can be controlled at below the 10ppm.This hydrolysate can be used for synthetic 107 glue through simple the processing, and cracking and the ring body rectifying two procedures that so can save original arts demand have greatly been saved production cost.
Experiment two:
Do the contrast experiment with the mixed reactor that the former mixed reactor of hydrolysis method process using and the present invention of monomethyl dichlorosilane and trimethylchlorosilane pre-composition and water executes example three, reaction medium is a water.
Adopt former mixed reactor, behind monomethyl dichlorosilane and trimethylchlorosilane premix, pre-composition and water directly enter in the reaction unit by the flow of 100L/h and 1000L/h respectively, 0 ℃～40 ℃ of control hydrolysis temperature.Hydrolysate is through physical sepn, and oil phase obtains containing hydrogen silicone oil through neutralization after the filtration.The containing hydrogen silicone oil analytical results sees the following form two.
Adopt the mixed reactor of the embodiment of the invention three, behind monomethyl dichlorosilane and trimethylchlorosilane premix, pre-composition enters into the pump chamber 7 of the forced circulation pump of loop by 100L/h after shower nozzle distributes, water enters in the reaction unit by the flow of 1000L/h, 0 ℃～40 ℃ of control hydrolysis temperature.Hydrolysate is through physical sepn, and oil phase obtains containing hydrogen silicone oil through neutralization after the filtration.The containing hydrogen silicone oil analytical results sees the following form two.
Table two
| Reaction unit | Acid content (ppm) | Hydrogen richness (%) |
| Former mixed reactor | 303 | 1.39 |
| Mixed reactor of the |
11 | 1.58 |
Claims (8)
1. halogenated silanes and reaction medium mixed reactor, comprise the loop that connects to form through connecting tube (5) by the import (20) of forced circulation device (2) and outlet (21), described loop is provided with halogenated silanes supplying opening (11), reaction medium supplying opening (12) and loop outlet (13), loop outlet (13) is after the outlet (21) of forced circulation device (2), the import (20) that reaction medium supplying opening (12) is arranged on forced circulation device (2) before, halogenated silanes is located to mix in halogenated silanes loop import (6) with reaction medium, it is characterized in that: connecting tube (5) import (20) last or forced circulation device (2) that described halogenated silanes loop import (6) is arranged between reaction medium supplying opening (12) and the forced circulation device (2) is located, and also is provided with diverting device (4) between described halogenated silanes supplying opening (11) and halogenated silanes loop import (6).
2. halogenated silanes as claimed in claim 1 and reaction medium mixed reactor is characterized in that: described forced circulation device (2) is a pump, and described halogenated silanes loop import (6) is arranged in its pump chamber (7).
3. halogenated silanes as claimed in claim 1 or 2 and reaction medium mixed reactor is characterized in that: described diverting device (4) is a liquid phase distributor.
4. halogenated silanes as claimed in claim 1 or 2 and reaction medium mixed reactor is characterized in that: described diverting device (4) is a shower nozzle.
5. halogenated silanes as claimed in claim 1 or 2 and reaction medium mixed reactor is characterized in that: be provided with interchanger (3) in the described loop, described interchanger (3) is arranged between the outlet (21) and loop outlet (13) of forced circulation device (2).
6. halogenated silanes as claimed in claim 5 and reaction medium mixed reactor, it is characterized in that: be provided with line mixer (1) between the import (20) of described forced circulation device (2) and the loop outlet (13), the reaction medium supplying opening (12) of loop is arranged on the line mixer (1).
7. utilize the halogenated silanes and the reaction medium hybrid reaction method of claim 1 or 2 described halogenated silanes and reaction medium mixed reactor, reaction medium enters loop by reaction medium supplying opening (12), described loop is connected to form through connecting tube (5) with outlet (21) by the import (20) of forced circulation device (2), and under forced circulation device (2) effect, circulate, it is characterized in that: halogenated silanes is behind diverting device (4), in the connecting tube (5) between reaction medium supplying opening (12) and forced circulation device (2), or give birth to reaction at the import (20) of forced circulation device (2) and reaction medium hybrid concurrency.
8. halogenated silanes as claimed in claim 7 and reaction medium hybrid reaction method is characterized in that:
Described halogenated silanes structural formula is: R
ySiX
4-y,
Wherein: R is C
nH
m, n is 〉=0 integer; M is 〉=1 integer, and y=1,2 or 3, X are halogen atom;
Described reaction medium is water, aqueous hydrochloric acid, methanol aqueous solution, aqueous sodium carbonate, sodium chloride aqueous solution or aqueous sodium hydroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102612771A CN101921397B (en) | 2010-08-24 | 2010-08-24 | Device and method for mixing and reacting halogenated silane with reaction medium |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102612771A CN101921397B (en) | 2010-08-24 | 2010-08-24 | Device and method for mixing and reacting halogenated silane with reaction medium |
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| Publication Number | Publication Date |
|---|---|
| CN101921397A true CN101921397A (en) | 2010-12-22 |
| CN101921397B CN101921397B (en) | 2012-04-18 |
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|---|---|---|---|
| CN2010102612771A Expired - Fee Related CN101921397B (en) | 2010-08-24 | 2010-08-24 | Device and method for mixing and reacting halogenated silane with reaction medium |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003477A (en) * | 2019-05-20 | 2019-07-12 | 张巧枝 | A kind of polydimethylsiloxane safe production equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB211247A (en) * | 1922-11-24 | 1924-02-21 | William Henry Raven | Improvements relating to the engines and power transmission mechanism of motor-cycles |
| CN85100433A (en) * | 1985-04-01 | 1986-07-23 | 吉林化学工业公司研究院 | New process of hydrolyzing organochlorosilanes |
| CN1271299A (en) * | 1997-09-25 | 2000-10-25 | Ge拜尔硅股份有限公司 | Device and method for producing silicones emulsions |
-
2010
- 2010-08-24 CN CN2010102612771A patent/CN101921397B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB211247A (en) * | 1922-11-24 | 1924-02-21 | William Henry Raven | Improvements relating to the engines and power transmission mechanism of motor-cycles |
| CN85100433A (en) * | 1985-04-01 | 1986-07-23 | 吉林化学工业公司研究院 | New process of hydrolyzing organochlorosilanes |
| CN1271299A (en) * | 1997-09-25 | 2000-10-25 | Ge拜尔硅股份有限公司 | Device and method for producing silicones emulsions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003477A (en) * | 2019-05-20 | 2019-07-12 | 张巧枝 | A kind of polydimethylsiloxane safe production equipment |
| CN110003477B (en) * | 2019-05-20 | 2021-09-14 | 胡海明 | Safe production equipment for polydimethylsiloxane |
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|---|---|
| CN101921397B (en) | 2012-04-18 |
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Effective date of registration: 20160311 Address after: 646606 Luzhou City, Sichuan province Longmatan District luohanzhen mud dam village Sheng silicon industry (Luzhou) Co. Ltd. Patentee after: Hesheng silicon industry (Luzhou) Co., Ltd. Address before: 646003 Luzhou city of Sichuan province Luzhou dam North Chemical Industry Co. Ltd. Patentee before: Luzhou Beifang Chemical Industry Co., Ltd. |
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