CN103071517B - Catalyst for producing calcium oxide by decomposing calcium sulfate and preparation method of catalyst - Google Patents
Catalyst for producing calcium oxide by decomposing calcium sulfate and preparation method of catalyst Download PDFInfo
- Publication number
- CN103071517B CN103071517B CN201310035685.9A CN201310035685A CN103071517B CN 103071517 B CN103071517 B CN 103071517B CN 201310035685 A CN201310035685 A CN 201310035685A CN 103071517 B CN103071517 B CN 103071517B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxide
- molecular sieve
- calcium sulfate
- decomposes
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000292 calcium oxide Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- 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 29
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- 239000003426 co-catalyst Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 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
- 238000012360 testing method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
The invention discloses a catalyst for producing calcium oxide by decomposing calcium sulfate and a preparation method of the catalyst. The catalyst comprises the following raw materials: 10-20wt% of main active component, namely iron oxide, 3-7wt% of cocatalyst, namely alumina, and 63-87wt% of molecular sieve. The invention further comprises the preparation method of the catalyst. The Fe2O3/Al2O3/molecular sieve catalyst for producing calcium oxide by decomposing calcium sulfate is high in catalytic activity, facilitates increasing a reaction rate when calcium sulfate is decomposed to produce calcium oxide, reduces the energy consumption, and lowers the cost.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, especially relate to a kind of calcium sulfate and decompose the Catalysts and its preparation method producing calcium oxide.
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, existing calcium sulfate decomposes generation sulfuric acid, is calcium sulfate Direct Resolution under weak oxide atmosphere or the two atmosphere effect of redox is produced sulfuric acid, and 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.Therefore, select suitable catalyst to accelerate reaction rate, be conducive to reducing energy consumption, reduce production cost.The carrier of custom catalysts is diatomite, and containing impurity in general diatomite, directly has influence on the activity of catalyst, restriction catalytic effect, but diatomite dedoping step in earlier stage comprises the processes such as washing-acid treatment-filtration-drying, very complicated, and cannot ensure that impurity eliminates completely.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, provides one to improve reaction efficiency, and the calcium sulfate reducing production cost decomposes the Catalysts and its preparation method producing calcium oxide.
The present invention solve the technical problem adopted technical scheme:
The calcium sulfate of the present invention decomposes the catalyst producing calcium oxide, is made up: main active component iron oxide (Fe of the raw material of following mass percent
2o
3) 10-20wt%, co-catalyst aluminium oxide (Al
2o
3) 3-7wt%, molecular sieve 63-87wt%, each raw material weight percentage sum is 100%.
Preferred mass percent is: main active component iron oxide (Fe
2o
3) 15wt%, co-catalyst aluminium oxide (Al
2o
3) 5wt%, molecular sieve 80wt%.
The calcium sulfate of the present invention decomposes the preparation method of the catalyst producing calcium oxide, comprises the following steps:
(1) by main active component iron oxide (Fe
2o
3) 10-20wt%, co-catalyst aluminium oxide (Al
2o
3) 3-7wt%, under normal temperature in high mixer the preferred 30min of blended 20-40min(), obtain Fe
2o
3/ Al
2o
3two component co-mixing systems;
(2) by step (1) gained Fe
2o
3/ Al
2o
3two component co-mixing systems, under normal temperature, roll the preferred 35min of 30-40min(in roller), impel Fe
2o
3, Al
2o
3particle Breakage, and mix, stand-by;
(3) will through the Fe of step (2) process gained
2o
3/ Al
2o
3molecular sieve high bake temperature in curer of second-component system and 63-87wt%, temperature is set to 1560-1600 DEG C (preferably 1580 DEG C), and the time of curing is the preferred 35min of 30-40min(), make Fe
2o
3/ Al
2o
3melt altogether, and redistribute in molecular sieve surface, obtain Fe
2o
3/ Al
2o
3/ molecular sieve catalyst.
According to Chinese invention patent application 200810058186.0, calcium sulfate decomposes generation calcium oxide, and 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↑
In this reaction, by adding the obtained Fe of the present invention
2o
3/ Al
2o
3/ molecular sieve catalyst, the mass ratio of catalyst and calcium sulfate controls at 1-3:2-6 (preferred 1:4), and reaction temperature controls at 500-700 DEG C (preferably 600 DEG C).
The carrier of the present invention's use is molecular sieve, has impayable special performance.Molecular sieve outer surface amasss the Al far above routine
2o
3, the material 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; Molecular sieve pore passage is regular, generally has three-dimensional communication duct, for reactant and product molecule provide wide space, improves reactant and the diffusion rate of product in duct, improves catalytic efficiency; And this zeolite molecular sieve carrier can remove moisture recycling.
The calcium sulfate of the present invention's use decomposes the Fe producing calcium oxide
2o
3/ Al
2o
3/ molecular sieve catalyst, catalytic activity high (calculating according to formula 1-1), is conducive to improving calcium sulfate and decomposes the reaction rate of producing calcium oxide, reduce energy consumption, reduce costs.
(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 of the present embodiment decomposes the catalyst producing calcium oxide, is made up: main active component iron oxide (Fe of following raw material
2o
3) 1kg, co-catalyst aluminium oxide (Al
2o
3) 0.3kg, molecular sieve 8.7kg.
Preparation method, comprises the following steps:
(1) by main active component iron oxide (Fe
2o
3) 1kg, co-catalyst aluminium oxide (Al
2o
3) 0.3kg, under normal temperature in high mixer blended 20min, obtain Fe
2o
3/ Al
2o
3two component co-mixing systems;
(2) by step (1) gained Fe
2o
3/ Al
2o
3two component co-mixing systems, under normal temperature, roll 30min, impel Fe in roller
2o
3, Al
2o
3particle Breakage, and mix, stand-by;
(3) will through the Fe of step (2) process gained
2o
3/ Al
2o
3molecular sieve high bake temperature in curer of second-component system and 8.7kg, temperature is set to 1560 DEG C, and the time of curing is 30min, makes Fe
2o
3/ Al
2o
3melt altogether, and redistribute in molecular sieve surface, obtain Fe
2o
3/ Al
2o
3/ molecular sieve catalyst.
According to Chinese invention patent application 200810058186.0, calcium sulfate decomposes the Fe adding the present embodiment in the reaction producing calcium oxide
2o
3-Al
2o
3/ molecular sieve catalyst system, the mass ratio of catalyst system and calcium sulfate controls at 1:6, and reaction temperature controls at 500 DEG C.
Embodiment 2
The calcium sulfate of the present embodiment decomposes the catalyst producing calcium oxide, is made up: main active component iron oxide (Fe of the raw material of following mass percent
2o
3) 2kg, co-catalyst aluminium oxide (Al
2o
3) 0.7kg, molecular sieve 7.3kg.
Preparation method, comprises the following steps:
(1) by main active component iron oxide (Fe
2o
3) 2kg, co-catalyst aluminium oxide (Al
2o
3) 0.7kg, under normal temperature in high mixer blended 40min, obtain Fe
2o
3/ Al
2o
3two component co-mixing systems;
(2) by step (1) gained Fe
2o
3/ Al
2o
3two component co-mixing systems, under normal temperature, roll 40min, impel Fe in roller
2o
3, Al
2o
3particle Breakage, and mix, stand-by;
(3) will through the Fe of step (2) process gained
2o
3/ Al
2o
3molecular sieve high bake temperature in curer of second-component system and 7.3kg, temperature is set to 1600 DEG C, and the time of curing is 40min, makes Fe
2o
3/ Al
2o
3melt altogether, and redistribute in molecular sieve surface, obtain Fe
2o
3/ Al
2o
3/ molecular sieve catalyst.
According to Chinese invention patent application 200810058186.0, calcium sulfate decomposes the Fe adding the present embodiment in the reaction producing calcium oxide
2o
3-Al
2o
3/ molecular sieve catalyst system, the mass ratio of catalyst system and calcium sulfate controls at 3:2, and reaction temperature controls at 700 DEG C.
Embodiment 3
The calcium sulfate of the present embodiment decomposes the catalyst producing calcium oxide, is made up: main active component iron oxide (Fe of the raw material of following mass percent
2o
3) 1.5kg, co-catalyst aluminium oxide (Al
2o
3) 0.5kg, molecular sieve 8kg.
Preparation method, comprises the following steps:
(1) by main active component iron oxide (Fe
2o
3) 1.5kg, co-catalyst aluminium oxide (Al
2o
3) 0.5kg, under normal temperature in high mixer blended 30min, obtain Fe
2o
3/ Al
2o
3two component co-mixing systems;
(2) by step (1) gained Fe
2o
3/ Al
2o
3two component co-mixing systems, under normal temperature, roll 35min, impel Fe in roller
2o
3, Al
2o
3particle Breakage, and mix, stand-by;
(3) will through the Fe of step (2) process gained
2o
3/ Al
2o
3molecular sieve high bake temperature in curer of second-component system and 8kg, temperature is set to 1580 DEG C, and the time of curing is 35min, makes Fe
2o
3/ Al
2o
3melt altogether, and redistribute in molecular sieve surface, obtain Fe
2o
3/ Al
2o
3/ molecular sieve catalyst.
According to Chinese invention patent application 200810058186.0, calcium sulfate decomposes the Fe adding the present embodiment in the reaction producing calcium oxide
2o
3-Al
2o
3/ molecular sieve catalyst system, the mass ratio of catalyst system and calcium sulfate controls at 1:4, and reaction temperature controls at 600 DEG C.
By embodiment 1-3 gained Fe
2o
3-Al
2o
3/ molecular sieve catalyst product carries 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 | 73 | 118 |
Embodiment 2 | 81 | 114 |
Embodiment 3 | 89 | 123 |
S108 | 53 | 100 |
Claims (5)
1. a calcium sulfate decomposes the catalyst producing calcium oxide, it is characterized in that, be made up of the raw material of following mass percent: main active component iron oxide 10-20wt%, co-catalyst aluminium oxide 3-7wt%, molecular sieve 63-87wt%, each raw material weight percentage sum is 100%;
Described calcium sulfate decomposes the preparation method of the catalyst producing calcium oxide, comprises the following steps:
(1) by main active component iron oxide 10-20wt%, co-catalyst aluminium oxide 3-7wt%, under normal temperature in high mixer blended 20-40min, obtain Fe
2o
3/ Al
2o
3two component co-mixing systems;
(2) by step (1) gained Fe
2o
3/ Al
2o
3two component co-mixing systems, under normal temperature, roll 30-40min, impel Fe in roller
2o
3, Al
2o
3particle Breakage, and mix, stand-by;
(3) will through the Fe of step (2) process gained
2o
3/ Al
2o
3molecular sieve high bake temperature in curer of second-component system and 63-87wt%, temperature is set to 1560-1600 DEG C, and the time of curing is 30-40min, makes Fe
2o
3/ Al
2o
3melt altogether, and redistribute in molecular sieve surface, obtain Fe
2o
3/ Al
2o
3/ molecular sieve catalyst.
2. calcium sulfate according to claim 1 decomposes the catalyst producing calcium oxide, it is characterized in that, is made up of the raw material of following mass percent: main active component iron oxide 15wt%, co-catalyst aluminium oxide 5wt%, molecular sieve 80wt%.
3. calcium sulfate according to claim 1 and 2 decomposes the catalyst producing calcium oxide, it is characterized in that, in the step (1) of described preparation method, and blended 30min in high mixer.
4. calcium sulfate according to claim 1 and 2 decomposes the catalyst producing calcium oxide, and it is characterized in that, in the step (2) of described preparation method, the time of rolling is 35min.
5. calcium sulfate according to claim 1 and 2 decomposes the catalyst producing calcium oxide, and it is characterized in that, in the step (3) of described preparation method, the temperature of high bake temperature is set to 1580 DEG C, and the time of curing is 35min.
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CN201310035685.9A CN103071517B (en) | 2013-01-30 | 2013-01-30 | Catalyst for producing calcium oxide by decomposing calcium sulfate and preparation method of catalyst |
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CN103071517A CN103071517A (en) | 2013-05-01 |
CN103071517B true CN103071517B (en) | 2015-04-15 |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2222740A (en) * | 1937-04-15 | 1940-11-26 | Chemische Werke Vorm H & E Alb | Production of sulphur dioxide from calcium sulphate |
CN1049299A (en) * | 1989-08-10 | 1991-02-20 | 杭州大学 | Sulfur-bearing organic catalyst to burned waste gas and preparation method thereof |
CN101186281A (en) * | 2007-12-10 | 2008-05-28 | 云南民族大学 | Method for reducing phosphogypsum decomposition temperature in process of preparing sulfuric acid from phosphogypsum |
CN101462699A (en) * | 2009-01-05 | 2009-06-24 | 昆明理工大学 | Catalytic reduction method for decomposing phosphogypsum by high-sulphur coal |
CN102583260A (en) * | 2012-02-13 | 2012-07-18 | 刘立文 | Method for decomposing anhydrite |
-
2013
- 2013-01-30 CN CN201310035685.9A patent/CN103071517B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2222740A (en) * | 1937-04-15 | 1940-11-26 | Chemische Werke Vorm H & E Alb | Production of sulphur dioxide from calcium sulphate |
CN1049299A (en) * | 1989-08-10 | 1991-02-20 | 杭州大学 | Sulfur-bearing organic catalyst to burned waste gas and preparation method thereof |
CN101186281A (en) * | 2007-12-10 | 2008-05-28 | 云南民族大学 | Method for reducing phosphogypsum decomposition temperature in process of preparing sulfuric acid from phosphogypsum |
CN101462699A (en) * | 2009-01-05 | 2009-06-24 | 昆明理工大学 | Catalytic reduction method for decomposing phosphogypsum by high-sulphur coal |
CN102583260A (en) * | 2012-02-13 | 2012-07-18 | 刘立文 | Method for decomposing anhydrite |
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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 |