CN211394648U - Chlorate decomposition process device in production of caustic soda by ion-exchange membrane method - Google Patents
Chlorate decomposition process device in production of caustic soda by ion-exchange membrane method Download PDFInfo
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- CN211394648U CN211394648U CN202020064636.3U CN202020064636U CN211394648U CN 211394648 U CN211394648 U CN 211394648U CN 202020064636 U CN202020064636 U CN 202020064636U CN 211394648 U CN211394648 U CN 211394648U
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Abstract
The utility model discloses a chlorate decomposes process units in ionic membrane process caustic soda production, mainly by chlorate heat exchanger, chlorate decomposer, chlorate pump A, chlorate pump B, electrolysis anode circulating groove, anode circulating pump A, anode circulating pump B, the governing valve, a flowmeter, acid concentration instrument, refined brine house steward constitutes, there is the chlorate heat exchanger chlorate decomposer import pipeline in front of, there is the chlorate pump on the outlet pipeline, electrolysis anode circulating groove import links to each other with the chlorate decomposer through chlorate pump and accessory pipeline, electrolysis anode circulating groove export has the anode circulating pump, its outlet pipeline distributes to the dechlorination tower, refined brine house steward, chlorate decomposer import pipeline, there is the flowmeter on the light brine pipeline of refined brine house steward, acid concentration instrument, the governing valve, realize after part strong acid light brine of chlorate export directly adds the circulating groove, chlorate export acid light brine can fully mix with electrolysis trough export light brine, the dechlorination system is more stable to control.
Description
Technical Field
The utility model relates to a chlorate production process in the industrial ionic membrane method caustic soda production field, in particular to a chlorate decomposition process device in the ionic membrane method caustic soda production.
Background
At present, the well-known ion-membrane method caustic soda production process technology is mature. The long-period operation of the production of caustic soda by the ion-membrane method is not intermittent, the brine in the caustic soda production can generate chlorate in the whole system, the chlorate is accumulated continuously, and the concentration of the chlorate is higher, so that the concentration of sodium chloride in the brine can be reduced, the current efficiency and the electrolysis quality of an electrolytic cell are influenced, and the chlorate has higher harm to the whole electrolytic system and seriously influences the production safety and the high efficiency. The weak brine (NaCl concentration: 205-. The qualified weak brine is adjusted to carry out chlorate decomposition in a chlorate decomposition tank through baffling delay (chemical reaction equation: NaClO3+6HCl =3Cl2+ NaCl +3H 2O), chlorine gas (the purity is more than or equal to 95%) produced by the reaction is merged into an electrolytic chlorine gas main pipe, if the purity is insufficient when the electrolytic chlorine gas main pipe is started and stopped, the chlorine gas is switched to a waste chlorine harm removal pipeline from the chlorine removal gas main pipe, and sodium hypochlorite produced after alkali absorption can be sold or used in the next process. The light brine at the outlet is pumped into a dechlorinating tower by a chlorate pump to carry out vacuum dechlorination and chemical dechlorination, and then is sent to a primary brine working section to be recycled. The problems that exist at present are:
1. because the acidity of the acidic light salt water at the outlet of the chlorate decomposition tank device is larger, the acidic light salt water is added into the inlet of the dechlorination tower to be mixed with the electrolytic dechlorinated light salt water (PH is more than or equal to 2 and less than or equal to 4), the flow of the chlorate decomposition device can not be increased because the dechlorination tower has the PH index requirement (PH is more than or equal to 1.1 and less than or equal to 1.5), otherwise, the PH at the inlet of the dechlorination tower exceeds the standard, and the strong acid salt.
2. When the ionic membrane operates to the later stage, chlorate generated by side reaction of the electrolytic cell is increased, but the decomposition flow of the chlorate decomposing device is limited and cannot be increased, the chlorate content of a salt water system is increased, the chlorate content in the liquid caustic soda is also increased, the quality of a liquid caustic soda product is influenced, the chlorate also causes corrosion damage to subsequent caustic soda evaporating device equipment, the maintenance cost of the equipment is increased, and the economic benefit of a chlor-alkali system is influenced.
Disclosure of Invention
The utility model aims to provide a do benefit to chlorate and decompose, improve the utilization ratio, reduce equipment cost of maintenance's process units who is fit for chlorate decomposition in the production of ion membrane method caustic soda.
In order to achieve the above object, the utility model provides a chlorate decomposes technology method in ion membrane method caustic soda production, its purpose aims at overcoming prior art's defect, realizes chlorate and subsequent production technology method, includes following step:
and 6, electrolyzing the brine distributed in each electrolytic tank, wherein the electrolyzed light brine automatically flows to an electrolytic anode circulating tank, is mixed with the strong acid light brine at the outlet part of the chlorate device, is sent to a dechlorination tower for vacuum physical dechlorination and chemical dechlorination, and is sent to primary brine hydrate salt.
And 7, leading the outlet of the anode circulating pump at the outlet of the electrolytic anode circulating tank to a salt water pipeline with the mass fraction of 75% to a dechlorinating tower, leading 15% of salt water to a refined salt water main pipe, and leading 10% of salt water to the inlet of the chlorate decomposing tank.
Further, in the step 1, the temperature of the dilute brine is controlled to be 88 ℃ through heat exchange from a chlorate heat exchanger, and then hydrochloric acid solution with the mass concentration of 31Wt% and the acidity of 0.45-0.55 mol/L is added and enters a chlorate decomposition tank.
Further, the liquid level of the chlorate decomposing tank in the step 1 is between 1.8 and 2.0 m.
Furthermore, in the step 1, the content of the fresh brine ClO 3-at the inlet of the chlorate decomposition tank is controlled to be less than or equal to 5 g/L, and the content of the fresh brine ClO 3-at the outlet of the chlorate decomposition tank is controlled to be less than or equal to 7 mg/L.
Further, in the step 1, the flow meter, the acid concentration meter and the regulating valve are controlled, the flow of the saline water fed by the flow meter is used as an auxiliary regulating parameter, the acidity of the dilute saline water controlled by the acid concentration meter is used as a main regulating parameter to regulate and output the regulating valve, and the regulating valve is set to be in cascade regulation.
Furthermore, the control of the adjusting valve of the acidity of the dilute brine and the automatic control program are manual control and automatic control, when the automatic control is put into operation, presetting the acidity and flow target set value of the main saturated refined brine pipe, presetting the acidity target value and flow target value, regulating the small valve opening value of a valve by the set value, generally presetting the small valve opening to be less than 25%, automatically judging whether the acidity of the main saturated refined brine pipe is within the acidity target value +/-0.2 by the system, if not, checking whether the system device is abnormal or not, controlling the acidity within the range of the acidity target value +/-0.2, and simultaneously judging whether the flow rate is larger than the flow rate target value or not, if the flow is less than one half of the target flow, presetting the small valve position control adjustment of the adjusting valve as manual operation, setting the small valve position opening value adjustment with the opening value opened by 3 times, and entering a cascade control stage; if the acidity is within the range of the acidity target value +/-0.2 and the flow is more than three-fourths of the flow target set value, the preset regulating valve small valve position is regulated to be manual, the small valve position opening value which is 0.8 times the opening value is set for regulation, and then the cascade control stage enters the fine regulation stage.
Further, the chemical dechlorination in the step 4 is to add the light salt brine into a sodium sulfite solution with the mass concentration of 4%.
Furthermore, in the step 5, the pH value of part of the strong-acid chlorine-containing weak brine is controlled to be more than or equal to 1.1 and less than or equal to 1.5.
A preparation device for chlorate decomposition process method in production of caustic soda by ion-exchange membrane method mainly comprises: the chlorate heat exchanger, the chlorate decomposer, the chlorate pump A, the chlorate pump B, the electrolytic anode circulating tank, the anode circulating pump A, the anode circulating pump B, the regulating valve, the flowmeter, the acid concentration instrument and the refined brine header pipe, wherein the chlorate heat exchanger is arranged in front of an inlet pipeline of the chlorate decomposer, the chlorate pump A and the chlorate pump B are arranged on an outlet pipeline, an inlet of the electrolytic anode circulating tank is connected with the chlorate decomposer through the chlorate pump and an auxiliary pipeline, the anode circulating pump A and the anode circulating pump B are arranged at an outlet of the electrolytic anode circulating tank, an outlet pipeline of the anode circulating pump is distributed to the dechlorination tower, the refined brine header pipe and an inlet pipeline of the chlorate decomposer, and the flowmeter, the acid concentration instrument and the regulating valve are arranged on a light brine.
The chlorate heat exchanger is arranged in front of an inlet pipeline of the chlorate decomposer, and the inlet of the chlorate heat exchanger is a light brine sodium chloride pipeline from a first-stage anode circulating pump and a light brine sodium chloride pipeline from a second-stage anode circulating pump.
The chlorate decomposing tank is provided with an inlet connected with an outlet pipeline of the chlorate heat exchanger and an outlet connected with the chlorate pump.
The chlorate pump is provided with an inlet connected with an outlet pipeline of the chlorate decomposition tank, an outlet connected with an outlet pipeline of the anode circulating pump and an inlet pipeline of the electrolysis anode circulating tank, or is directly distributed to the dechlorination tower, the refined brine header pipe and the inlet pipeline of the chlorate decomposition tank,
the inlet of the electrolytic anode circulating tank is connected with the light salt brine at the outlet of the chlorate decomposing tank through the outlet of the chlorate pump, and the outlet of the electrolytic anode circulating tank is distributed to the dechlorinating tower, the refined salt brine main pipe and the inlet pipeline of the chlorate decomposing tank.
The inlet of the flowmeter, the acid concentration meter and the regulating valve is connected with the outlet of an anode circulating pump of the electrolytic anode circulating tank, or is directly connected with the light salt water at the outlet of the chlorate decomposing tank through the outlet of the chlorate pump,
Preferably, the electrolytic anode circulation tank can be put into the chlorate decomposition system as required.
The beneficial effects of the utility model reside in that: the utility model provides a chlorate decomposition process method in production of caustic soda by ion membrane method, simple process has following advantage compared in traditional technology:
1. the chlorate pump outlet brine is added into the anode circulating tank or goes to a main pipe for protecting refined brine, so that the decomposition amount of the chlorate decomposing tank can be greatly increased, and the original limitation of the PH (1.1-1.5) index range can not improve the chlorate decomposition amount any more.
2. After part of the chlorate outlet strong acid light salt brine is directly added into the circulating tank, the chlorate outlet strong acid light salt brine can be fully mixed with the chlorate outlet light salt brine of the electrolytic tank, and the PH control of a dechlorination system is more stable.
3. Part of strong-acid weak brine at the chlorate outlet goes to the protective refined brine main pipe to replace the original weak brine, and the PH of the brine entering the saturated refined brine main pipe and then entering each electrolytic cell is reduced, so that the addition amount of high-purity hydrochloric acid as an auxiliary material of the electrolytic cell can be reduced, and the consumption of the auxiliary material is saved.
4. After the decomposition amount of the chlorate decomposing device is increased, newly increased chlorate in side reaction of the electrolytic cell can be balanced, the quality of liquid caustic soda and caustic soda flakes is improved, the corrosion influence on a subsequent caustic soda flakes device is relieved, the whole chlor-alkali system keeps good operation, the abnormal opening and shutdown times are reduced, the inspection and maintenance times are reduced, the investment in equipment maintenance and replacement is reduced, and the labor intensity is reduced.
5. The improved process can bring considerable direct economic benefit and recessive benefit for chlor-alkali enterprises, and simultaneously the method provided by the utility model has the advantages of simple process, low cost and high direct yield, and is suitable for large-scale popularization and application in production.
Drawings
FIG. 1 is a schematic view of the process and the apparatus used in the process of chlorate decomposition in caustic soda production by ion-exchange membrane method.
In fig. 1: 1 is a chlorate heat exchanger; 2 is a chlorate decomposer; 3 is chlorate pump A; 4 is chlorate pump B; 5 is an electrolytic anode circulating tank; 6 is an anode circulating pump A; 7 is an anode circulating pump B; 8 is a flowmeter; 9 is an acid concentration instrument; 10 is a regulating valve; 11 is a refined brine main pipe;
a is light salt brine sodium chloride from a first-stage anode circulating pump;
b is dilute brine sodium chloride from a secondary anode circulating pump;
c is a chlorine gas harm removal header pipe;
d is a chlorine and dechlorination gas main pipe;
e is light salt water from an ionic membrane electrolytic cell;
f is the brine with the mass fraction of 75 percent and is sent to a dechlorination tower;
g is saline water with the mass fraction of 15 percent;
h is 10 percent of saline water in percentage by mass and goes to the inlet of the chlorate decomposer.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
Referring to the attached fig. 1, in order to achieve the above object, embodiment 1 of the present invention provides a chlorate decomposition process in production of caustic soda by using an ion membrane method, which aims to overcome the defects of the prior art, and realize chlorate decomposition and subsequent production process, and comprises the following steps:
and 6, electrolyzing the brine distributed in each electrolytic tank, wherein the electrolyzed light brine automatically flows to an electrolytic anode circulating tank, is mixed with the strong acid light brine at the outlet part of the chlorate device, is sent to a dechlorination tower for vacuum physical dechlorination and chemical dechlorination, and is sent to primary brine hydrate salt.
And 7, leading the outlet of an anode circulating pump A6 or B7 at the outlet of the electrolytic anode circulating tank 5 to a salt water pipeline with the mass fraction of 75% to a dechlorination tower, leading 15% of salt water to a refined salt water main pipe, and leading 10% of salt water to the inlet of the chlorate decomposition tank.
Further, in the step 1, the chlorate heat exchanger 1 is used, the temperature of the dilute brine is controlled to exchange heat to 88 ℃, hydrochloric acid solution with the mass concentration of 31Wt% and the acidity of 0.45-0.55 mol/L is added, and the mixture enters a chlorate decomposition tank.
Further, the liquid level of the chlorate decomposing tank 2 in the step 1 is between 1.8 and 2.0 m.
Furthermore, in the step 1, the content of ClO 3-in the light salt brine at the inlet of the chlorate decomposer 2 is controlled to be less than or equal to 5 g/L, and the content of ClO 3-in the light salt brine at the outlet of the chlorate decomposer 2 is controlled to be less than or equal to 7 mg/L.
Furthermore, in the step 1, the flow meter 8, the acid concentration meter 9 and the regulating valve 10 are controlled, the flow rate of the brine fed by the flow meter 8 is used as an auxiliary regulating parameter, the acidity of the dilute brine controlled by the acid concentration meter 9 is used as a main regulating parameter to regulate and output the regulating valve 10, and the regulating valve 10 is set to be in cascade regulation.
Furthermore, the control of the adjusting valve of the acidity of the dilute brine and the automatic control program are manual control and automatic control, when the automatic control is put into operation, presetting the acidity and flow target set value of the main saturated refined brine pipe, presetting the acidity target value and flow target value, regulating the small valve opening value of a valve 10 by the set value, generally presetting the small valve opening to be less than 25 percent, automatically judging whether the acidity of the main saturated refined brine pipe is within the acidity target value +/-0.2 by the system, if not, checking whether the system device is abnormal or not, controlling the acidity within the range of the acidity target value +/-0.2, and simultaneously judging whether the flow rate is larger than the flow rate target value or not, if the flow is less than one half of the target flow, the preset regulating valve 10 is adjusted to be manual, the opening value is set to be opened by 3 times, and then the cascade control stage is started; if the acidity is within the range of the acidity target value +/-0.2 and the flow is more than three-fourths of the flow target set value, the preset regulating valve 10 is adjusted to be manual in small valve position opening value regulation, the opening value is set to be 0.8 times opened, and then the cascade control stage enters a fine adjustment stage. For example, the preset acidity target value is 1.3, the flow target value is 15m3/h, the set value regulating valve 10 has a small valve opening value of 20%, the preset small valve opening is generally less than 25%, the system automatically judges whether the acidity of the saturated refined brine header pipe is 1.3 +/-0.2, if the acidity is not in the range, the system device is checked whether the system device is abnormal, if the acidity is in the range of 1.3 +/-0.2, the system simultaneously judges whether the flow is more than 20m3/h, and the flow is less than one half of the target set value 10 m3/h, the preset regulating valve 10 has a small valve opening value which is manually adjusted, the small valve opening value which is 3 times the opening value is set to be 60% for adjustment, and then the cascade control stage is carried out; if the acidity is in the range of 1.3 +/-0.2 and the flow target set value is three-quarters 15m3/h, the preset regulating valve 10 is adjusted to be manual in small valve position control, the opening value is set to be opened by 0.8 times, the small valve position opening value is adjusted by 16%, and then the cascade control stage is started to enter the fine adjustment stage.
Further, the chemical dechlorination in the step 4 is to add the light salt brine into a sodium sulfite solution with the mass concentration of 4%.
Furthermore, in the step 5, the pH value of part of the strong-acid chlorine-containing weak brine is controlled to be more than or equal to 1.1 and less than or equal to 1.5.
A preparation device for chlorate decomposition process method in production of caustic soda by ion-exchange membrane method mainly comprises: the chlorate decomposition device comprises a chlorate heat exchanger 1, a chlorate decomposition tank 2, a chlorate pump A3, a chlorate pump B4, an electrolytic anode circulation tank 5, an anode circulation pump A6, an anode circulation pump B7, a flow meter 8, an acid concentration instrument 9, a regulating valve 10 and a refined brine header pipe 11, wherein the chlorate heat exchanger 1 is arranged in front of an inlet pipeline of the chlorate decomposition tank 2, the chlorate pump A3 and the chlorate pump B4 are arranged on an outlet pipeline, the inlet of the electrolytic anode circulation tank 5 is connected with the chlorate decomposition tank 2 through the chlorate pump 3 or 4 and an auxiliary pipeline, the anode circulation pump A6 and the anode circulation pump B7 are arranged at the outlet of the electrolytic anode circulation tank 5, the outlet pipeline of the anode circulation pump A6 or B7 is distributed to a dechlorination tower, the refined brine header pipe 11 and an inlet pipeline of the chlorate decomposition tank, and the flow meter 8, the acid concentration instrument 9 and the regulating valve.
The chlorate heat exchanger 1 is arranged in front of an inlet pipeline of the chlorate decomposer 2, and the inlet of the chlorate heat exchanger is a light brine sodium chloride pipeline from a first-stage anode circulating pump and a light brine sodium chloride pipeline from a second-stage anode circulating pump.
The chlorate decomposing tank 2 is provided with an inlet connected with an outlet pipeline of the chlorate heat exchanger 1, and an outlet connected with a chlorate pump A3 or B4.
The chlorate pump A3 or B4 is provided with an inlet connected with an outlet pipeline of the chlorate decomposing tank 2, and an outlet connected with an outlet pipeline of the anode circulating pump A6 or B7 and an inlet pipeline of the electrolysis anode circulating tank 5, or directly distributed to the dechlorinating tower, the refined brine header pipe 11 and the inlet pipeline of the chlorate decomposing tank.
The inlet of the electrolytic anode circulating tank 5 is connected with the light salt brine at the outlet of the chlorate decomposing tank through the outlet of the chlorate pump, and the outlet of the electrolytic anode circulating tank is distributed to the dechlorinating tower, the refined salt brine main pipe 11 and the inlet pipeline of the chlorate decomposing tank.
The inlet of the flowmeter 8, the acid concentration meter 9 and the regulating valve 10 is connected with the outlet of an anode circulating pump A6 or B7 of the electrolytic anode circulating tank 5, or directly connected with the outlet of the dilute brine of the chlorate decomposing tank 2 through the outlet of a chlorate pump A3 or B4.
Preferably, the electrolytic anode circulation tank 2 may be put into the chlorate decomposition system as needed.
The foregoing is a preferred embodiment of the present invention and it should be understood that it is not intended to be exhaustive or to limit the invention to the precise form disclosed, and that modifications and enhancements may be made by those skilled in the art without departing from the principles of the present invention in order to better illustrate the principles and practice of the invention and to enable those skilled in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (7)
1. Chlorate decomposition process units in ion-exchange membrane process caustic soda production, its characterized in that: the device mainly comprises a chlorate heat exchanger, a chlorate decomposition tank, a chlorate pump A, a chlorate pump B, an electrolytic anode circulation tank, an anode circulation pump A, an anode circulation pump B, a regulating valve, a flow meter, an acid concentration instrument and a refined brine header pipe, wherein the chlorate heat exchanger is arranged in front of an inlet pipeline of the chlorate decomposition tank, the chlorate pump A and the chlorate pump B are arranged on an outlet pipeline, an inlet of the electrolytic anode circulation tank is connected with the chlorate decomposition tank through the chlorate pump and an auxiliary pipeline, the anode circulation pump A and the anode circulation pump B are arranged at an outlet of the electrolytic anode circulation tank, an outlet pipeline of the anode circulation pump is distributed to a dechlorination tower, the refined brine header pipe and the chlorate decomposition tank, and the flow meter, the acid concentration instrument and the regulating valve are arranged on a light brine pipeline of.
2. The process unit for decomposing chlorate in the production of caustic soda by the ion-membrane method as claimed in claim 1, wherein: the chlorate heat exchanger is arranged in front of an inlet pipeline of the chlorate decomposer, and the inlet of the chlorate heat exchanger is from a light brine sodium chloride pipeline of the first-stage anode circulating pump and a light brine sodium chloride pipeline of the second-stage anode circulating pump.
3. The process unit for decomposing chlorate in the production of caustic soda by the ion-membrane method as claimed in claim 1, wherein: the chlorate decomposing tank is provided with an inlet connected with an outlet pipeline of the chlorate heat exchanger and an outlet connected with the chlorate pump.
4. The process unit for decomposing chlorate in the production of caustic soda by the ion-membrane method as claimed in claim 1, wherein: the chlorate pump is provided with an inlet connected with an outlet pipeline of the chlorate decomposition tank, and an outlet connected with an outlet pipeline of the anode circulating pump and an inlet pipeline of the electrolysis anode circulating tank, or directly distributed to the dechlorination tower, the refined brine header pipe and the inlet pipeline of the chlorate decomposition tank.
5. The process unit for decomposing chlorate in the production of caustic soda by the ion-membrane method as claimed in claim 1, wherein: the inlet of the electrolytic anode circulating tank is connected with the light salt brine at the outlet of the chlorate decomposing tank through the outlet of the chlorate pump, and the outlet of the electrolytic anode circulating tank is distributed to the dechlorinating tower, the refined salt brine main pipe and the inlet pipeline of the chlorate decomposing tank.
6. The process unit for decomposing chlorate in the production of caustic soda by the ion-membrane method as claimed in claim 1, wherein: the inlet of the flowmeter, the acid concentration meter and the regulating valve is connected with the outlet of an anode circulating pump of the electrolysis anode circulating tank, or is directly connected with the outlet of the chlorate decomposing tank to discharge the light salt water through the outlet of the chlorate pump.
7. The process unit for decomposing chlorate in the production of caustic soda by the ion-membrane method as claimed in claim 1, wherein: the electrolytic anode circulating tank is put into a chlorate decomposing system according to the requirement.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111074293A (en) * | 2020-01-14 | 2020-04-28 | 石河子天域新实化工有限公司 | Chlorate decomposition process in production of caustic soda by ion-exchange membrane method |
| CN114293207A (en) * | 2021-11-19 | 2022-04-08 | 宁夏金昱元能源化学有限公司 | System and method for decomposing chlorate in caustic soda production by ion-exchange membrane method |
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2020
- 2020-01-14 CN CN202020064636.3U patent/CN211394648U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111074293A (en) * | 2020-01-14 | 2020-04-28 | 石河子天域新实化工有限公司 | Chlorate decomposition process in production of caustic soda by ion-exchange membrane method |
| CN111074293B (en) * | 2020-01-14 | 2022-05-10 | 石河子天域新实化工有限公司 | Chlorate decomposition process in production of caustic soda by ion-exchange membrane method |
| CN114293207A (en) * | 2021-11-19 | 2022-04-08 | 宁夏金昱元能源化学有限公司 | System and method for decomposing chlorate in caustic soda production by ion-exchange membrane method |
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Effective date of registration: 20210423 Address after: North Road 832000 the Xinjiang Uygur Autonomous Region Shihezi City Development Zone No. 36 Patentee after: TIANCHEN CHEMICAL Co.,Ltd. Patentee after: SHIHEZI TIANYU XINSHI CHEMICAL Co.,Ltd. Patentee after: XINJIANG TIANYE (Group) Co.,Ltd. Address before: 832000 county level administrative division of Xinjiang Uygur Autonomous Region Patentee before: SHIHEZI TIANYU XINSHI CHEMICAL Co.,Ltd. Patentee before: XINJIANG TIANYE (Group) Co.,Ltd. |