CN103111317B - Catalyst utilizing calcium sulfate to decompose and produce sulfuric acid and preparation method thereof - Google Patents
Catalyst utilizing calcium sulfate to decompose and produce sulfuric acid and preparation method thereof Download PDFInfo
- Publication number
- CN103111317B CN103111317B CN201310035531.XA CN201310035531A CN103111317B CN 103111317 B CN103111317 B CN 103111317B CN 201310035531 A CN201310035531 A CN 201310035531A CN 103111317 B CN103111317 B CN 103111317B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sulfuric acid
- calcium sulfate
- sodium sulphate
- vanadic anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 52
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 30
- 239000002808 molecular sieve Substances 0.000 claims abstract description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010457 zeolite Substances 0.000 claims abstract description 24
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 25
- 239000003426 co-catalyst Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 10
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 description 1
- YXXYPPNYZBASJN-UHFFFAOYSA-N [Si].[Na].[K].[V] Chemical compound [Si].[Na].[K].[V] YXXYPPNYZBASJN-UHFFFAOYSA-N 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- -1 diatomite vanadium series Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a catalyst utilizing calcium sulfate to decompose and produce sulfuric acid and a preparation method thereof. The catalyst is prepared by the following raw materials according to mass percent: 25-40 wt% of main active component, vanadic oxide, 25-35 wt% of cocatalyst sodium sulfate, and 25-50 wt% of carrier zeolite molecular sieve. The invention also discloses a preparation method of a catalyst. The catalyst utilizing the calcium sulfate to decompose and produce the sulfuric acid provided by the invention can improve the speed that sulfur dioxide is converted into sulfuric anhydride by catalyzing and oxidizing, the production efficiency is improved, and the energy consumption is reduced.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, especially relate to a kind of calcium sulfate that utilizes and decompose the Catalysts and its preparation method producing sulfuric acid.
Background technology
Along with the development of human society, the energy is more and more nervous, and the comprehensive utilization of various circles of society to the energy is more and more paid attention to.At present, utilize calcium sulfate to decompose and produce sulfuric acid, be that calcium sulfate Direct Resolution under weak oxide atmosphere or the two atmosphere effect of redox is produced sulfuric acid, actual decomposition temperature is all more than 1000 DEG C, refractory material in separation equipment is difficult to reach requirement, and energy resource consumption is larger.Oxidizing sulfur dioxide becomes sulfur trioxide to prepare sulfuric acid, mainly utilizes vanadium series catalyst, and it is with V
2o
5for active component, with alkali-metal sulfate (K
2sO
4or Na
2sO
4) for co-catalyst, take diatomite as the multicomponent catalyst of carrier, be commonly referred to as vanadium-potassium (sodium)-silicon System Catalyst, this kind of catalyst requirement carrier diatomaceous earth must be pure, and containing the impurity such as aluminium oxide, iron oxide in general diatomite, directly have influence on the activity of catalyst, restriction catalytic effect, but, diatomaceous dedoping step is complicated, and cannot ensure to eliminate completely.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, and the calcium sulfate that utilizes providing a kind of activity high decomposes the Catalysts and its preparation method producing sulfuric acid.
The present invention solve the technical problem adopted technical scheme:
The calcium sulfate that utilizes of the present invention decomposes the catalyst producing sulfuric acid, is made up: main active component vanadic anhydride (V of the raw material of following mass percent
2o
5) 25-40wt%, co-catalyst sodium sulphate (Na
2sO
4) 25-35wt%, carrier zeolite molecular sieve 25-50wt%.
Preferred mass percent is: main active component vanadic anhydride (V
2o
5) 30wt%, co-catalyst sodium sulphate (Na
2sO
4) 30wt%, carrier zeolite molecular sieve 40wt%.
The calcium sulfate that utilizes of the present invention decomposes the preparation method of the catalyst producing sulfuric acid, comprises the following steps:
(1) at normal temperatures, by the main active component vanadic anhydride of 25-40wt%, the co-catalyst sodium sulphate of 25-35wt%, premixed 30-40min (preferred 35min) in high speed blender, the mixture of winner's active component vanadic anhydride and co-catalyst sodium sulphate;
(2) in the mixture of step (1) winner of institute active component vanadic anhydride and co-catalyst sodium sulphate, add the carrier zeolite molecular sieve of 25-50wt%, then stir 40-60min (preferably 50 min), form uniform ternary mixture;
(3) by step (2) gained ternary mixture, at normal temperatures, utilize roller to roll 30-50min, make each component further evenly blended;
(4) by step (3) gained mixture, high bake temperature in curer, temperature controls at 500-700 DEG C (preferably 600 DEG C), and the time of curing is 80-110min (preferred 100min), obtains vanadic anhydride-sodium sulphate/zeolite molecular sieve catalyst.
According to Chinese invention patent application 200810058186.0, calcium sulfate decomposes generation sulfur dioxide (SO
2), its reaction principle is as follows:
CaSO
4+2C=CaS+2CO
2↑
CaSO
4+4CO=CaS+4CO
2↑
CaS+2O
2=CaSO
4↑
2CaS+3O
2=2CaO+2SO
2↑
CaS+3CaSO
4=4CaO+4SO
2↑
Under the effect of the vanadic anhydride-sodium sulphate/zeolite molecular sieve catalyst of gained of the present invention, sulfur dioxide and oxygen react and generate sulfur trioxide under high-temperature and high-pressure conditions, then by concentrated sulfuric acid solution, be converted into sulfuric acid, its reaction principle is as follows:
Catalyst prepared by the present invention, the carrier of use is zeolite molecular sieve, and zeolitic molecular sieve has impayable special performance, and zeolite molecular sieve outer surface amasss the Al far above routine
2o
3, the materials such as diatomite, high-specific surface area is conducive to the high degree of dispersion of active component, improves the load capacity of active component; And zeolite molecular sieve duct is regular, generally there is three-dimensional communication duct, for reactant and product molecule provide spacious space, improve reactant and the diffusion rate of product in duct, reach the effect improving catalytic efficiency; And this zeolite molecular sieve carrier can realize recycling by removing moisture.
The calcium sulfate that utilizes of the present invention decomposes the catalyst producing sulfuric acid, can improve the speed that sulfur dioxide Catalytic Oxygen changes into sulfur trioxide, enhance productivity, reduce energy consumption.
Note: the active testing of this catalyst adopts formula 1-1 to calculate.
(1-1)
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The calcium sulfate that utilizes of the present embodiment decomposes the catalyst producing sulfuric acid, is made up: main active component vanadic anhydride 2.8kg, co-catalyst sodium sulphate 3.0kg, carrier zeolite molecular sieve 4.2kg of the raw material of following mass percent.
Preparation method, comprises the following steps:
(1) at normal temperatures, by the main active component vanadic anhydride of 2.8kg, 3.0kg co-catalyst sodium sulphate, premixed 30min in high speed blender, the mixture of winner's active component vanadic anhydride and co-catalyst sodium sulphate;
(2) in the mixture of step (1) winner of institute active component vanadic anhydride and co-catalyst sodium sulphate, add the carrier zeolite molecular sieve of 4.2kg, then stir 40min, form uniform ternary mixture;
(3) by step (2) gained ternary mixture, at normal temperatures, utilize roller to roll 30min, make each component further evenly blended;
(4) by step (3) gained mixture, high bake temperature in curer, temperature controls at 500 DEG C, and the time of curing is 80min, obtains vanadic anhydride-sodium sulphate/zeolite molecular sieve catalyst.
Embodiment 2
The calcium sulfate that utilizes of the present embodiment decomposes the catalyst producing sulfuric acid, is made up: main active component vanadic anhydride 2.5kg, co-catalyst sodium sulphate 3.5kg, carrier zeolite molecular sieve 4kg of the raw material of following mass percent.
Preparation method, comprises the following steps:
(1) at normal temperatures, by the main active component vanadic anhydride of 2.5kg, 3.5kg co-catalyst sodium sulphate, premixed 40min in high speed blender, the mixture of winner's active component vanadic anhydride and co-catalyst sodium sulphate;
(2) mixture of past step (1) winner of institute active component vanadic anhydride and co-catalyst sodium sulphate adds the carrier zeolite molecular sieve of 4kg, then high-speed stirred 60min, forms uniform ternary mixture;
(3) by step (2) gained ternary mixture, at normal temperatures, utilize roller to roll 50min, and make each component further evenly blended;
(4) by step (3) gained mixture, high bake temperature in curer, temperature controls at 700 DEG C, and the time of curing is 110min, obtains vanadic anhydride-sodium sulphate/zeolite molecular sieve catalyst.
Embodiment 3
The calcium sulfate that utilizes of the present embodiment decomposes the catalyst producing sulfuric acid, is made up: main active component vanadic anhydride 3kg, co-catalyst sodium sulphate 3kg, carrier are zeolite molecular sieve 4kg of the raw material of following mass percent.
Preparation method, comprises the following steps:
(1) at normal temperatures, by the main active component vanadic anhydride of 3kg, 3kg co-catalyst sodium sulphate, premixed 35min in high speed blender, the mixture of winner's active component vanadic anhydride and co-catalyst sodium sulphate;
(2) in the mixture of step (1) winner of institute active component vanadic anhydride and co-catalyst sodium sulphate, add the carrier zeolite molecular sieve of 4kg, then stir 50min, form uniform ternary mixture;
(3) by step (2) gained ternary mixture, at normal temperatures, utilize roller to roll 40min, and make each component further evenly blended;
(4) by step (3) gained mixture, high bake temperature in curer, temperature controls at 600 DEG C, and the time of curing is 100min, obtains vanadic anhydride-sodium sulphate/zeolite molecular sieve catalyst.
Embodiment 1-3 gained vanadic anhydride-sodium sulphate/zeolite molecular sieve catalyst product is carried out strength character detection according to ASTM D6175-2003 (2008), and active in formula (1-1) calculating, testing result is in table 1.
Table 1 embodiment 1-3 product and vanadium-sodium/diatomite vanadium series catalyst (S108) the performance test results compare
| Activity/% | Intensity/N.cm-1 | |
| Embodiment 1 | 75 | 108 |
| Embodiment 2 | 68 | 105 |
| Embodiment 3 | 93 | 114 |
| S108 | 53 | 100 |
Claims (5)
1. utilize calcium sulfate to decompose the catalyst producing sulfuric acid, it is characterized in that, be made up of the raw material of following mass percent: main active component vanadic anhydride 25-40wt%, co-catalyst sodium sulphate 25-35wt%, carrier zeolite molecular sieve 25-50wt%;
The preparation method of described catalyst, comprises the following steps:
(1) at normal temperatures, by the main active component vanadic anhydride of 25-40wt%, the co-catalyst sodium sulphate of 25-35wt%, premixed 30-40min in high speed blender, the mixture of winner's active component vanadic anhydride and co-catalyst sodium sulphate;
(2) in the mixture of step (1) winner of institute active component vanadic anhydride and co-catalyst sodium sulphate, add the carrier zeolite molecular sieve of 25-50wt%, then stir 40-60min, form uniform ternary mixture;
(3) by step (2) gained ternary mixture, at normal temperatures, utilize roller to roll 30-50min, make each component further evenly blended;
(4) by step (3) gained mixture, high bake temperature in curer, temperature controls at 500-700 DEG C, and the time of curing is 80-110min, obtains vanadic anhydride-sodium sulphate/zeolite molecular sieve catalyst.
2. the calcium sulfate that utilizes according to claim 1 decomposes the catalyst producing sulfuric acid, it is characterized in that, be made up of the raw material of following mass percent: main active component vanadic anhydride 30wt%, co-catalyst sodium sulphate 30wt%, carrier zeolite molecular sieve 40wt%.
3. the calcium sulfate that utilizes according to claim 1 and 2 decomposes the catalyst producing sulfuric acid, and it is characterized in that, in its preparation methods steps (1), the time of premixed in high speed blender is 35min.
4. the calcium sulfate that utilizes according to claim 1 and 2 decomposes the catalyst producing sulfuric acid, and it is characterized in that, in its preparation methods steps (2), the time of stirring is 50min.
5. the calcium sulfate that utilizes according to claim 1 and 2 decomposes the catalyst producing sulfuric acid, and it is characterized in that, in its preparation methods steps (4), in curer, the temperature of high bake temperature controls at 600 DEG C, and the time of curing is 100min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310035531.XA CN103111317B (en) | 2013-01-30 | 2013-01-30 | Catalyst utilizing calcium sulfate to decompose and produce sulfuric acid and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310035531.XA CN103111317B (en) | 2013-01-30 | 2013-01-30 | Catalyst utilizing calcium sulfate to decompose and produce sulfuric acid and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103111317A CN103111317A (en) | 2013-05-22 |
| CN103111317B true CN103111317B (en) | 2015-05-13 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345531A (en) * | 2016-08-23 | 2017-01-25 | 安徽海德石油化工有限公司 | Catalyst for converting sulfur dioxide into sulfur trioxide in waste sulfuric acid cracking and regeneration process |
| CN110255507A (en) * | 2019-08-02 | 2019-09-20 | 青岛惠城信德新材料研究院有限公司 | A kind of Waste Sulfuric Acid regeneration method |
| CN112010347B (en) * | 2020-07-23 | 2022-07-26 | 中信锦州金属股份有限公司 | Method for improving yield by precipitating vanadium from high-chromium vanadium solution ammonium salt |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049299A (en) * | 1989-08-10 | 1991-02-20 | 杭州大学 | Sulfur-bearing organic catalyst to burned waste gas and preparation method thereof |
| CN101850262A (en) * | 2010-05-26 | 2010-10-06 | 吉林省临江市天元催化剂有限公司 | Preparation method of SO2 oxidizing reaction catalyst |
| CN102153106A (en) * | 2010-07-29 | 2011-08-17 | 兰州理工大学 | Quick reparation method for heteroatom phosphorus aluminum molecular sieve in eutectoid |
| CN102350367A (en) * | 2011-08-30 | 2012-02-15 | 开封市三丰催化剂有限责任公司 | Production method of sulfuric acid catalyst by oxidizing sulfur dioxide |
-
2013
- 2013-01-30 CN CN201310035531.XA patent/CN103111317B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049299A (en) * | 1989-08-10 | 1991-02-20 | 杭州大学 | Sulfur-bearing organic catalyst to burned waste gas and preparation method thereof |
| CN101850262A (en) * | 2010-05-26 | 2010-10-06 | 吉林省临江市天元催化剂有限公司 | Preparation method of SO2 oxidizing reaction catalyst |
| CN102153106A (en) * | 2010-07-29 | 2011-08-17 | 兰州理工大学 | Quick reparation method for heteroatom phosphorus aluminum molecular sieve in eutectoid |
| CN102350367A (en) * | 2011-08-30 | 2012-02-15 | 开封市三丰催化剂有限责任公司 | Production method of sulfuric acid catalyst by oxidizing sulfur dioxide |
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Effective date of registration: 20160825 Address after: An Industrial Park Economic Development Zone, Changde City, Hunan province Linli County 415200 Patentee after: Hunan Fu Xiang new type building material Co., Ltd. Address before: 410005, 12 floor, Haidong mansion, Furong Road, Changsha, Hunan Patentee before: Liu Liwen |