CN106800310A - Method using tail powder preparation trivalent tiron is calcined - Google Patents
Method using tail powder preparation trivalent tiron is calcined Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
- C01G23/0534—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts in the presence of seeds
Abstract
The present invention relates to a kind of sulfuric acid method titanium pigment production technology, a kind of method using tail powder preparation trivalent tiron is calcined is specifically disclosed, comprised the following steps：A, the powder mashing of calcining tail；B, to tail powder starch in add the ammonium sulfate and the concentrated sulfuric acid of metering to be dissolved more than 120 DEG C；C, dilution cooling solution, to the aluminium powder that metering is added in dilution, obtain trivalent tiron.It is an advantage of the invention that：1) recovery of titanium resource in calcining tail powder is realized；2) there is provided a kind of method for preparing trivalent tiron with accessory substance calcining tail powder, titanium white production cost is reduced；3) the method combination sulfuric acid method titanium pigment production craft step realizes the ingenious recovery of calcining tail powder, and method is easy, beneficial to industrially promoting.
Description
Technical field
The present invention relates to a kind of titanium white production technique, especially a kind of sulfuric acid method titanium pigment production technology.
Background technology
Titanium dioxide is a kind of important Inorganic Chemicals, most wide as most important, range of application because refractive index is high
Chinese white, since being succeeded in developing from the fifties of last century four, quickly grown, instead of traditional white face such as lithopone
Material, accounts for more than the 80% of whole Chinese white usage amounts, nontoxic, harmless, is widely used in coating, plastics, papermaking, off-set oil
The industries such as ink, chemical fibre, rubber, cosmetics, food.Titanium white production technique mainly has two kinds of sulfuric acid process and chloridising, China's life
Production. art is based on sulfuric acid process.Further investigation and optimization sulfate process titanium dioxide powder craft, realize that maximally utilizing for internal resource is
The emphasis of the research of current sulfate process titanium dioxide powder craft.Typical sulfuric acid method titanium pigment technological process can be summarized as follows：
(1) acidolysis reaction is carried out with sulfuric acid with ilmenite concentrate or acid-dissolved titanium slag, obtains titanyl sulfate solution；
(2) hydrolysing titanyl sulfate solution obtains thick metatitanic acid slurry；
(3) thick metatitanic acid slurry is washed, salt treatment, obtain pretreatment metatitanic acid；
(4) pretreatment metatitanic acid feeding rotary kiln calcining output titanium dioxide base-material.
(5) titanium dioxide base-material is obtained titanium dioxide product by postprocessing working procedures.
Wherein, the technique that thick metatitanic acid slurry is washed is specially：
(1) once wash：Separation of solid and liquid is carried out to thick metatitanic acid slurry, a filter cake is obtained；Water-filling is entered to a filter cake
Wash to remove wherein iron ion, obtain one and wash metatitanic acid cake；One washes metatitanic acid cake adds water mashing, obtains one and washes metatitanic acid slurry；
(2) bleaching reduction：Being washed in metatitanic acid slurry toward one adds bleaching agent and reducing agent to be bleached, and adds calcining brilliant
Kind, obtain bleaching slurry；
(3) secondary washing：Separation of solid and liquid is carried out to bleaching slurry, secondary filter cake is obtained；Secondary filter cake is washed with
Further removal wherein iron ion, obtains two and washes metatitanic acid cake；Two wash metatitanic acid cake adds water mashing, obtains two and washes metatitanic acid material
Slurry.
In sulfuric acid method titanium pigment production process, iron tramp the prolonging with washing time in metatitanic acid after once washing
Long, acidity reduction, is gradually oxidized, and exists in the form of solid high ferro, cannot be removed by washing, is converted to Fe/
TiO2Ratio in 500~1000ppm or so.But if iron is not removed thoroughly, the Trace Iron in metatitanic acid by after high-temperature calcination,
Red di-iron trioxide is generated, rutile lattice is mixed into, causes lattice deformability, produce lattice defect, form chromophoric activity point,
So that product whiteness and reducing power decline, the optical property of titanium dioxide is had influence on, make product rutile titanium white powder that yellow is presented.Cause
During this production rutile titanium white powder, it is necessary to carry out (see above-mentioned steps 2) after bleaching reduction to once washing metatitanic acid slurry, then lead to
Secondary water is crossed to wash away except the impurity iron being mixed in metatitanic acid.Method general at present is bleached using sulfuric acid, is then adopted
Reduced with trivalent tiron, Fe/TiO can be made after secondary washing20~30ppm is reduced to, the whiteness of finished product titanium dioxide is obtained
It is significant to improve.
Trivalent tiron for reducing is usually trivalent titanium solution, and its usual production method is：Take metatitanic acid mashing system
Into certain density slurry, then the concentrated sulfuric acid is added to be dissolved in the case of heating stirring.Then reaction is down to necessarily
After temperature, add water to be diluted to finite concentration, then be dividedly in some parts aluminium powder titanyl sulfate is reduced to titanous, obtain titanous molten
Liquid.Wherein the solution temperature of metatitanic acid generally needs to reach 110 DEG C.
In sulfuric acid method titanium pigment production process, titanyl sulfate by hydrolysis, one wash, bleach, two washing, before salt treatment, kiln
Enter calcining rotary kiln after press filtration to be calcined, by dehydration, desulfurization, be converted into anatase titanium dioxide, further turn after calcining
Turn to rutile titanium dioxide.During calcining, generally with natural gas or coal gas as the energy, by air heat
Kiln tail is taken to from combustion chamber, air quantity is up to a few all places/hours, in this course, substantial amounts of dust in kiln can be taken to kiln tail,
And this part dust collection is returned eventually through tail gas spray and dust arrester, this part dust is calcining tail powder.Calcining
Contain a large amount of rutile titanium dioxides, anatase titanium dioxide, metatitanic acid in tail powder, up to 10~30ppm is also contained in addition
Cr and the nearly Fe of 100ppm (being shown in Table 1), it is difficult to recycle.Because calcining tail powder impurity content is higher, if being directly mixed in
Metatitanic acid filter cake is pre-processed before kiln to be reclaimed, then can influence product quality, if after being directly appended to kiln, can be because of salinity
It is too high, influence mashing viscosity and product quality.
Table 1：A certain calcining tail powder Main elements analysis
| Fe(ppm) | S(ppm) | Cr(ppm) | |
| 86.4 | 80.2 | 19000 | 9.7 |
From table 1 it follows that calcining tail powder in contain substantial amounts of titanium, with recovery value, but simultaneously impurity content compared with
Many, purification difficulty is big, and industrially by-product recovery needs emphasis to consider economy, there is no economically viable calcining tail powder to return at present
Receiving method.
The content of the invention
For economic recovery calcines tail powder, the invention provides a kind of method using tail powder preparation trivalent tiron is calcined.
The technical solution adopted in the present invention is：Method using tail powder preparation trivalent tiron is calcined, including following step
Suddenly：
A, calcining tail powder mashing is taken, obtain tail powder slurry；
B, starched to tail powder in add the concentrated sulfuric acid and ammonium sulfate of metering, and the temperature of slurry is increased to more than 120 DEG C,
Tail powder is starched fully dissolving, obtain tail powder solution；
C, dilute and cool down tail powder solution, obtain dilution, to adding the aluminium powder of metering in dilution by dilution four
Valency titanium is reduced to titanous, obtains trivalent tiron.
Inventor's proposition in the present invention, can reclaim calcining using the similar method by metatitanic acid preparation trivalent titanium solution
Tail powder, but it is different, and the main component of metatitanic acid slurry is metatitanic acid, and in sulfuric acid solution, skewness acid is in fire-bar
Generation titanyl sulfate solution can be rapidly dissolved under part, the titanic in solution can be reduced into titanous by follow-up addition aluminium powder,
So as to obtain trivalent titanium solution.
And it is entirely not metatitanic acid to calcine in tail powder, and contain some inverted rutile titanium dioxides and sharp
Titanium-type titanium dioxide (both account for tail nearly 50%) of powder gross mass, and the chemical property of wherein rutile titanium dioxide is highly stable,
The concentrated sulfuric acid can be just only completely dissolved under the conditions of long-time is boiled, causes the method to be industrially difficult to carry out.
To solve this problem, inventor adds the ammonium sulfate of metering in the solution, and the addition of ammonium sulfate can be with sulfuric acid shape
Into azeotropic mixture, so as to improve the boiling point of solution, be conducive to accelerating the rate of dissolution of rutile titanium dioxide.
On the other hand, industry experience has been generally acknowledged that the recovery of accessory substance is needed useful component in accessory substance and impurity component
Separate, utilized so as to extract useful component.In the present invention inventor propose, without to calcining tail powder in impurity into
Dividing carries out any treatment, and the trivalent tiron for finally obtaining is actually the mixed solution containing impurity such as iron, cadmium, sulphur.Though contain
There are a large amount of impurity, but combine sulfuric acid method titanium pigment subsequent production technique, inventor proposes directly to be used as the trivalent tiron
Reducing agent, due to the presence of reproducibility titanous, wherein impurity component cannot form precipitation (for example iron can not be oxidized to solid
High ferro) so that the impurity eventually entered into bleaching slurry exists in the form of soluble-salt, and these impurity can be with follow-up solid-liquid
Separate and secondary washing step enters filtrate and wash water, separated so as to wash metatitanic acid cake with two, will not be to final titanium dioxide product
Quality impact.
As a further improvement on the present invention, step B is specially：The ammonium sulfate of metering is first added to tail powder slurry, then
The metering concentrated sulfuric acid is added with certain speed, the temperature of slurry is increased to more than 120 DEG C finally by heating, this programme first to
Tail powder slurry adds ammonium sulfate, then by controlling the concentration of the concentrated sulfuric acid and adding speed, makes full use of the heat of dilution of the concentrated sulfuric acid,
Slurry temperature is raised, is treated that the concentrated sulfuric acid is added and is finished, then slurry temperature is reached target temperature by supplementing steam, can played and subtract
The purpose of few energy consumption and Simplified flowsheet.
As a further improvement on the present invention, in step B ammonium sulfate (with (NH4)2SO4Meter) addition and tail powder starch
Middle titanium is (with TiO2Meter) mass ratio be m (NH4)2SO4:mTiO2=0.5~1.5:1.Ammonium sulfate addition is very few to sulfuric acid solution
The raising effect of boiling point is limited so that even if solution is heated into boiling rutile type titanium white can not be made comparatively fast to dissolve.Hair
A person of good sense show that ammonium sulfate addition, can be by the slurry elevation of boiling point to target temperature in above range through overtesting.In this area
It is interior, specific addition number also with tail powder slurry in titanium dioxide concentration and sulfuric acid concentration etc. it is relevant.
As a further improvement on the present invention, TiO in the tail powder slurry of step A2Content is 100g/L~500g/L.
As a further improvement on the present invention, in step B the concentrated sulfuric acid (with H2SO4Meter) addition and tail powder slurry in titanium
(with TiO2Meter) mass ratio be mH2SO4:mTiO2=3~8:1.
As a further improvement on the present invention, the mass concentration of the concentrated sulfuric acid is 85~98% in step B.
As a further improvement on the present invention, the temperature of dilution is 30~70 DEG C in step C.
As a further improvement on the present invention, in step C in the addition of aluminium powder and dilution titanium (with TiO2Meter) matter
Amount is than being mAl:mTiO2=0.08~0.15:1.
The beneficial effects of the invention are as follows：1) there is provided a kind of recovery method for calcining tail powder, titanium money in calcining tail powder is realized
The recovery in source, prevents from largely calcining tail powder heap product environment is polluted and the wasting of resources.2) there is provided a kind of trivalent tiron
Preparation method, the method calcines tail powder as raw material, reduces the consumption of metatitanic acid with accessory substance, reduce titanium white production into
This.3) the method need not carry out extra process to impurity in calcining tail point, be to combine sulfuric acid method titanium pigment production technology step
The targetedly by-product recovery scheme carried out on the basis of rapid, realizes the ingenious recovery of calcining tail powder, does not increase production cost,
Beneficial to industrially promoting.
Specific embodiment
With reference to embodiment, the present invention is further described.
Explanation：The degree of material refers both to mass percent without special instruction in following examples and comparative example.
Embodiment one：
Titanous reagent A is prepared using calcining tail powder in accordance with the following methods：
(1) calcining tail powder (TiO is taken2=86.4%, Fe=80.2ppm, S=19000ppm, Cr=9.7ppm) 1kg, plus
It is 114g/L that water is beaten to wherein content of titanium dioxide, obtains calcining tail powder slurry 7.58L.
(2) above-mentioned calcining tail powder slurry is placed in titanous preparation vessel, to addition 0.69kg solid ammonium sulfates in slurry,
Stirring is opened, slowly to adding 4.4kg98 acid, addition to finish in slurry, heating is opened and slurry is warming up to 122 DEG C, Ran Houbao
Warm 90min makes metatitanic acid and titanium dioxide in calcining tail powder be dissolved into titanyl sulfate solution.
(3) it is diluted with water and titanyl sulfate solution is cooled to 30 DEG C, is added altogether to point 3 batches in the solution after dilution
69g aluminium powders are well mixed, and are then incubated 40min, obtain titanous reagent A, and titanous reagent A composition is detected, are detected
The results are shown in Table 2.
Washing metatitanic acid slurry to one with titanous reagent A using following methods carries out reduction and prepares two to wash metatitanic acid slurry A：
(4) take 1000mL and treat that metatitanic acid slurry (TiO is washed in bleaching one2=300g/l), add above-mentioned titanous reagent A, 80g
98 acid and 12g calcining seeds, stir 100min under the conditions of 60 DEG C, bleaching detects the trivalent Ti content in solution after terminating
It is 0.52g/l, bleaching slurry obtains two and washes metatitanic acid slurry A through washing.Metatitanic acid slurry A compositions are washed to two and enters row element point
Analysis, testing result is shown in Table 3.
Embodiment two：
Trivalent tiron B is prepared using calcining tail powder in accordance with the following methods：
(1) calcining tail powder (TiO is taken2=86.4%, Fe=80.2ppm, S=19000ppm, Cr=9.7ppm) 1kg, plus
It is 487g/L that water is beaten to wherein content of titanium dioxide, obtains calcining tail powder slurry 1.77L.
(2) above-mentioned calcining tail powder slurry is placed in titanous preparation vessel, to addition 1.30kg solid ammonium sulfates in slurry,
Stirring is opened, slowly to the concentrated sulfuric acid that 8.1kg mass concentrations 85% are added in slurry, addition is finished, and opens heating by slurry liter
Temperature is incubated 60min to 165 DEG C, then makes metatitanic acid and titanium dioxide in calcining tail powder be dissolved into titanyl sulfate solution.
(3) it is diluted with water and titanyl sulfate solution is cooled to 70 DEG C, is added altogether to point 3 batches in the solution after dilution
86g aluminium powders are well mixed, and are then incubated 40min, obtain trivalent tiron B, and trivalent tiron B component is detected, are detected
The results are shown in Table 2.
Washing metatitanic acid slurry to one with trivalent tiron B using following methods carries out reduction and prepares two to wash metatitanic acid slurry B：
(4) take 1000mL and treat that metatitanic acid slurry (TiO is washed in bleaching one2=300g/l), the above-mentioned trivalent tiron B of addition,
80g98 acid and 12g calcining seeds, stir 100min under the conditions of 60 DEG C, and bleaching detects that the titanous in solution contains after terminating
It is 0.51g/l to measure, and bleaching slurry obtains two and washes metatitanic acid slurry B through washing.Metatitanic acid slurry B component is washed to two and enters row element point
Analysis, testing result is shown in Table 3.
Embodiment three：
Titanous reagent C is prepared using calcining tail powder in accordance with the following methods：
(1) calcining tail powder (TiO is taken2=86.4%, Fe=80.2ppm, S=19000ppm, Cr=9.7ppm) 1kg, plus
It is 309g/L that water is beaten to wherein content of titanium dioxide, obtains calcining tail powder slurry 2.80L.
(2) above-mentioned calcining tail powder slurry is placed in titanous preparation vessel, then to addition 0.43kg solid sulfurs in slurry
Sour ammonium, opens stirring, and slowly to the concentrated sulfuric acid that 2.79kg mass concentrations 93% are added in slurry, addition is finished, and opening heating will
Slurry is warming up to 145 DEG C, and insulation 80min makes metatitanic acid and titanium dioxide in calcining tail powder be dissolved into titanyl sulfate solution.
(3) it is diluted with water and titanyl sulfate solution is cooled to 60 DEG C, is added altogether to point 3 batches in the solution after dilution
128g aluminium powders are well mixed, and are then incubated 40min, obtain titanous reagent C, and titanous reagent C composition is detected, are detected
The results are shown in Table 2.
Washing metatitanic acid slurry to one with titanous reagent C using following methods carries out reduction and prepares two to wash metatitanic acid slurry C：
(4) take 1000mL and treat that metatitanic acid slurry (TiO is washed in bleaching one2=300g/l), the above-mentioned titanous reagent C of addition,
80g98 acid and 12g calcining seeds, stir 100min under the conditions of 60 DEG C, and bleaching detects that the titanous in solution contains after terminating
It is 0.50g/l to measure, and bleaching slurry obtains two and washes metatitanic acid slurry C through washing.Metatitanic acid slurry C compositions are washed to two and enters row element point
Analysis, testing result is shown in Table 3.
Comparative example four：
Titanous reagent D is prepared by metatitanic acid slurry using the following method：
(1) take one and wash metatitanic acid slurry (TiO2=300g/L) 5L, it is placed in titanous preparation vessel, slowly add in slurry
Enter 98 acid of 7.6kg, while open heating is increased to 110 DEG C by slurry temperature, insulation 90min is obtained titanyl sulfate solution.
(2) it is diluted with water and titanyl sulfate solution is cooled to 30 DEG C, is added altogether to point 3 batches in the solution after dilution
150g aluminium powders are well mixed, and are then incubated 40min, obtain titanous reagent D, and titanous reagent D composition is detected, are detected
The results are shown in Table 2.
Washing metatitanic acid slurry to one with titanous reagent D using following methods carries out reduction and prepares two to wash metatitanic acid slurry D：
(3) take 1000mL and treat that metatitanic acid slurry (TiO is washed in bleaching one2=300g/l), add above-mentioned titanous reagent D, 80g
98 acid and 12g calcining seeds, stir 100min under the conditions of 60 DEG C, bleaching detects the trivalent Ti content in solution after terminating
It is 0.50g/l, bleaching slurry obtains two and washes metatitanic acid slurry D through washing.Metatitanic acid slurry D compositions are washed to two and enters row element point
Analysis, testing result is shown in Table 3.
Table 2：Trivalent tiron testing result table
| Ti(g/L) | |
| Titanous reagent A | 56 |
| Trivalent tiron B | 90 |
| Titanous reagent C | 76 |
| Titanous reagent D | 70 |
Table 3：Two wash metatitanic acid slurry testing result table
| Fe(ppm) | Cr(ppm) | |
| Two wash metatitanic acid slurry A | 10 | 3.5 |
| Two wash metatitanic acid slurry B | 7 | 2.4 |
| Two wash metatitanic acid slurry C | 8 | 2.7 |
| Two wash metatitanic acid slurry D | 8 | 2.6 |
Claims (8)
1., using the method that tail powder prepares trivalent tiron is calcined, comprise the following steps：
A, calcining tail powder mashing is taken, obtain tail powder slurry；
B, starched to tail powder in add the ammonium sulfate and the concentrated sulfuric acid of metering, and the temperature of slurry is increased to more than 120 DEG C, make tail
The fully dissolving of powder slurry, obtains tail powder solution；
C, dilute and cool down tail powder solution, obtain dilution, to adding the aluminium powder of metering in dilution by titanic in dilution
Titanous is reduced to, trivalent tiron is obtained.
It is 2. according to claim 1 to utilize the method that tail powder prepares trivalent tiron of calcining, it is characterised in that：Step B has
Body is：The ammonium sulfate of metering is added in first being starched to tail powder, the concentrated sulfuric acid of metering is then added with given pace, finally by tail powder
Slurry is warming up to more than 120 DEG C.
It is 3. according to claim 1 to utilize the method that tail powder prepares trivalent tiron of calcining, it is characterised in that：In step B
Ammonium sulfate is (with (NH4)2SO4Meter) addition and tail powder slurry in titanium (with TiO2Meter) mass ratio be m (NH4)2SO4:mTiO2
=0.5~1.5:1.
4. the method that tail powder prepares trivalent tiron is calcined in the utilization according to any claim in claims 1 to 3, its
It is characterised by：The TiO of the tail powder slurry of step A2Content is 100g/L~500g/L.
5. the method that tail powder prepares trivalent tiron is calcined in the utilization according to any claim in claims 1 to 3, its
It is characterised by：The concentrated sulfuric acid is (with H in step B2SO4Meter) addition and tail powder slurry in titanium (with TiO2Meter) mass ratio be
mH2SO4:mTiO2=3~8:1.
6. the method that tail powder prepares trivalent tiron is calcined in the utilization according to any claim in claims 1 to 3, its
It is characterised by：The mass concentration of the concentrated sulfuric acid is 85~98% in step B.
7. the method that tail powder prepares trivalent tiron is calcined in the utilization according to any claim in claims 1 to 3, its
It is characterised by：The temperature of dilution is 30~70 DEG C in step C.
8. the method that tail powder prepares trivalent tiron is calcined in the utilization according to any claim in claims 1 to 3, its
It is characterised by：In step C in the addition of aluminium powder and dilution titanium (with TiO2Meter) mass ratio be mAl:mTiO2=0.08~
0.15:1。
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| CN108002435A (en) * | 2017-12-14 | 2018-05-08 | 四川龙蟒钛业股份有限公司 | A kind of method for improving the sulfuric acid method titanium pigment quality of production |
| CN108424670A (en) * | 2018-04-25 | 2018-08-21 | 四川龙蟒钛业股份有限公司 | A kind of method of the effective reuse of titanium white production waste material |
| CN112624186A (en) * | 2021-02-21 | 2021-04-09 | 甘肃东方钛业有限公司 | Method for preparing trivalent titanium by using electric dedusting material |
| CN115108583A (en) * | 2022-06-30 | 2022-09-27 | 陕西理工大学 | Aqueous phase dispersion of TiO 2 Method for preparing nanocrystalline |
| CN115124072A (en) * | 2022-07-05 | 2022-09-30 | 中国科学院宁波材料技术与工程研究所 | Method for preparing high-purity nano titanium dioxide by sulfuric acid process and product |
| CN115124072B (en) * | 2022-07-05 | 2024-04-26 | 中国科学院宁波材料技术与工程研究所 | Method for preparing high-purity nano titanium dioxide by sulfuric acid method and product |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108002435A (en) * | 2017-12-14 | 2018-05-08 | 四川龙蟒钛业股份有限公司 | A kind of method for improving the sulfuric acid method titanium pigment quality of production |
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| CN108424670A (en) * | 2018-04-25 | 2018-08-21 | 四川龙蟒钛业股份有限公司 | A kind of method of the effective reuse of titanium white production waste material |
| CN112624186A (en) * | 2021-02-21 | 2021-04-09 | 甘肃东方钛业有限公司 | Method for preparing trivalent titanium by using electric dedusting material |
| CN115108583A (en) * | 2022-06-30 | 2022-09-27 | 陕西理工大学 | Aqueous phase dispersion of TiO 2 Method for preparing nanocrystalline |
| CN115108583B (en) * | 2022-06-30 | 2023-08-22 | 陕西理工大学 | Aqueous dispersion of TiO 2 Method for preparing nanocrystalline |
| CN115124072A (en) * | 2022-07-05 | 2022-09-30 | 中国科学院宁波材料技术与工程研究所 | Method for preparing high-purity nano titanium dioxide by sulfuric acid process and product |
| CN115124072B (en) * | 2022-07-05 | 2024-04-26 | 中国科学院宁波材料技术与工程研究所 | Method for preparing high-purity nano titanium dioxide by sulfuric acid method and product |
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Address after: 618200 Mianzhu new town industrial concentration area, Sichuan, Deyang Patentee after: Longbai Sichuan Titanium Co., Ltd Address before: 618200 Mianzhu new town industrial concentration area, Sichuan, Deyang Patentee before: SICHUAN LOMON TITANIUM Co.,Ltd. |
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