CN103285875B - Solid-phase compound metal catalyst used for magnesium desulphurization technology - Google Patents
Solid-phase compound metal catalyst used for magnesium desulphurization technology Download PDFInfo
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- CN103285875B CN103285875B CN201310248369.XA CN201310248369A CN103285875B CN 103285875 B CN103285875 B CN 103285875B CN 201310248369 A CN201310248369 A CN 201310248369A CN 103285875 B CN103285875 B CN 103285875B
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Abstract
The invention discloses a solid-phase compound metal catalyst used for a magnesium desulphurization technology, belonging to the technical field of the preparation of compound metal catalysts. The catalyst is prepared through dissolving a divalent manganese salt, a divalent cobalt salt, a divalent copper salt, a divalent nickel salt, a trivalent iron salt and a trivalent bismuth salt in water, co-precipitating through using molybdate, drying, oven-drying, and calcining. The catalyst has the advantages of simple operation, substantial catalysis effect, realization of the increase of the system oxidation efficiency of above 50% without changing the original oxidation gas quantity, less application amount, easy recovery, less residual in the solution, and no secondary pollution problems, and has a popularization value.
Description
Technical field
The invention belongs to composite metallic catalyst preparing technical field, be specifically related to a kind of solid phase composite metallic catalyst for accessory substance magnesium sulfite oxidation in magnesium processes sulfur removal technology.Catalyst of the present invention is by improving the oxidizing reaction rate of magnesium sulfite, thus solve desulphurization system because of magnesium sulfite excessive concentration the problem of fouling and blocking, and effectively can reduce investment and the energy consumption of oxidative system, and the secondary pollution problem because using catalyst to cause.
Background technology
SO
2be the important predecessor causing the contamination phenomenon such as acid rain and gray haze, in recent years significant damage caused to China's atmospheric environment.Magnesium processes desulfurization is the flue gas treating process that current mediumand smallscale industrial boilers is conventional, but because the oxidation reaction of accessory substance sulphite is relatively slow, cause the investment of desulfurizing byproduct recovery process and energy consumption all higher, and the insufficient present situation of sulfite oxidation also easily causes, and scaling block, product qualities is low, relief liquor secondary pollution problems.
The hypodynamic Main Means of current solution desulphurization system energy of oxidation adds metal ion catalyst to improve the oxidation rate of magnesium sulfite.But because catalyst adds desulfurization slurry all in the form of a solution, cause the operating cost of application process higher, and catalyst difficulty reclaims and also will cause in desulfuration byproduct and exterior liquid and occur heavy metal secondary pollution phenomenon, therefore the application of catalyst is also greatly limited.
Summary of the invention
Instant invention overcomes the deficiency of existing liquid metal ionic catalyst, a kind of solid phase composite metallic catalyst for magnesium processes sulfur removal technology is provided.
For a solid phase composite metallic catalyst for magnesium processes sulfur removal technology, described catalyst is by water-soluble for the salt containing metal ion, and utilizes molybdate to make it co-precipitation, precipitation drying, oven dry, roasting is prepared from; The described salt containing metal ion is manganous salt, divalent cobalt, cupric salt, divalent nickel salt, trivalent iron salt and trivalent bismuth salt, and wherein the mass percent of metal ion manganese, cobalt, copper, bismuth, iron, nickel is: (1-5): (7-20): (2-10): (1-5): (2-10): 1.
In described catalyst, the mass percent of metal ion manganese, cobalt, copper, bismuth, iron, molybdenum, nickel is: (1-5): (7-20): (2-10): (1-5): (2-10): (14-60): 1.
Described manganous salt, divalent cobalt, cupric salt, divalent nickel salt, trivalent iron salt and trivalent bismuth salt be respectively in sulfate, nitrate and chloride one or more.
Described molybdate is one or more in sodium salt, ammonium salt and sylvite.
The condition of described drying is at 100 DEG C ~ 120 DEG C dry 8 ~ 12 hours.
The condition of described oven dry is dry 9 ~ 12 hours at 200 DEG C ~ 300 DEG C.
The condition of described last roasting is roasting 4 ~ 8 hours at 400 DEG C ~ 600 DEG C.
Catalyst preparation process of the present invention is simple, easy to operate.Compared with the existing technology, tool of the present invention has the following advantages: (1) solid-phase catalyst of the present invention preparation manipulation condition is simple.(2) solid catalysis effect of the present invention is comparatively remarkable, the oxidation rate of magnesium sulfite can be made to improve more than 50%, effectively can be applied to the optimization of magnesia FGD process oxidizes system.(3) use of the present invention can not cause negative effect to desulphurization system, also can promote that the forward of desulphurization reaction carries out because of accelerated oxidation reaction, thus improve desulfuration efficiency to a certain extent.(4) solid-phase catalyst consumption of the present invention is little, easily reclaims, residual few, produces secondary pollution problem hardly, it also avoid the wasting of resources.
Accompanying drawing explanation
Fig. 1 is solid-phase catalyst catalytic effect figure.
Detailed description of the invention
In order to be illustrated more clearly in the present invention, enumerate following examples, but it is without any restrictions to scope of the present invention.
The computational methods of rate of catalysis reaction:
Getting a certain amount of catalyst is added in magnesium sulfite oxidation system, at interval of the concentration of sulfate radical in a period of time assaying reaction device, represent the oxidizing reaction rate of magnesium sulfite with sulfate radical growing amount in the unit interval, the reaction rate of magnesium sulfite under catalytic condition can be obtained.
Embodiment 1
Take Co (NO
3)
26H
2o 1.798g, Cu (NO
3)
23H
2o 0.442g, Fe (NO
3)
39H
2o 1.265g, Bi (NO
3)
35H
2o 0.247g, Mn (NO
3)
20.48ml, Ni (NO
3)
26H
2o 0.233g, (NH
4)
3mo
7o
244H
2o 1.994g, is dissolved in respectively in 20ml deionized water at ambient temperature, mixes successively, stirs, water bath method, 120
odrying 8 hours under C condition, 300
odry 9 hours under C condition, 520
ounder C condition, roasting 5 hours, makes solid-phase catalyst.
Take above-mentioned catalyst 0.202g, add in magnesium sulfite oxidation reactor, reaction solution volume is 200ml, and now rate of catalysis reaction comparatively improves about 0.570 times without catalytic condition.
Embodiment 2
Take Co (NO
3)
26H
2o 1.949g, Cu (NO
3)
23H
2o 0.508g, Fe (NO
3)
39H
2o 1.951g, Bi (NO
3)
35H
2o 0.203g, Mn (NO
3)
20.52ml, Ni (NO
3)
26H
2o 0.226g, (NH
4)
3mo
7o
244H
2o 3.054g, is dissolved in respectively in 20ml deionized water at ambient temperature, mixes successively, stirs, water bath method, 120
odrying 8 hours under C condition, 300
odry 9 hours under C condition, 480
ounder C condition, roasting 5 hours, makes solid-phase catalyst.
Take above-mentioned catalyst 0.202g, add in magnesium sulfite oxidation reactor, reaction solution volume is 200ml, and now rate of catalysis reaction comparatively improves about 0.558 times without catalytic condition.
Embodiment 3
Take Co (NO
3)
26H
2o 2.005g, Cu (NO
3)
23H
2o 0.597g, Fe (NO
3)
39H
2o 1.840g, Bi (NO
3)
35H
2o 0.276g, Mn (NO
3)
20.49ml, Ni (NO
3)
26H
2o 0.260g, (NH
4)
3mo
7o
244H
2o 2.969g, is dissolved in respectively in 20ml deionized water at ambient temperature, mixes successively, stirs, water bath method, 120
odrying 8 hours under C condition, 300
odry 9 hours under C condition, 500
ounder C condition, roasting 5 hours, makes solid-phase catalyst.
Take above-mentioned catalyst 0.203g, add in magnesium sulfite oxidation reactor, reaction solution volume is 200ml, and now rate of catalysis reaction comparatively improves about 0.566 times without catalytic condition.
Embodiment 4
Take Co (NO
3)
26H
2o 1.998g, Cu (NO
3)
23H
2o 0.479g, Fe (NO
3)
39H
2o 1.550g, Bi (NO
3)
35H
2o 0.258g, Mn (NO
3)
20.44ml, Ni (NO
3)
26H
2o 0.243g, (NH
4)
3mo
7o
244H
2o 2.455g, is dissolved in respectively in 20ml deionized water at ambient temperature, mixes successively, stirs, water bath method, 100
odrying 12 hours under C condition, 200
odry 12 hours under C condition, 550
ounder C condition, roasting 5 hours, makes solid-phase catalyst.
Take above-mentioned catalyst 0.201g, add in magnesium sulfite oxidation reactor, reaction solution volume is 200ml, and now rate of catalysis reaction comparatively improves about 0.777 times without catalytic condition.
Embodiment 5
Take Co (NO
3)
26H
2o 1.803g, Cu (NO
3)
23H
2o 0.511g, Fe (NO
3)
39H
2o 1.616g, Bi (NO
3)
35H
2o 0.235g, Mn (NO
3)
20.54ml, Ni (NO
3)
26H
2o 0.215g, (NH
4)
3mo
7o
244H
2o 2.468g, is dissolved in respectively in 20ml deionized water at ambient temperature, mixes successively, stirs, water bath method, 100
odrying 12 hours under C condition, 200
odry 12 hours under C condition, 450
ounder C condition, roasting 8 hours, makes solid-phase catalyst.
Take above-mentioned catalyst 0.202g, add in magnesium sulfite oxidation reactor, reaction solution volume is 200ml, and now rate of catalysis reaction comparatively improves about 1.698 times without catalytic condition.
The catalytic reaction effect of embodiment 1 ~ 5 is as shown in Figure 1: " case0 " represents the course of reaction of magnesium sulfite oxidation under on-catalytic condition, and " case1 ~ case5 " represents the course of reaction of magnesium sulfite oxidation under the catalyst condition of embodiment 1 ~ 5 respectively.Reaction condition is as follows: reaction solution volume 200ml, 35 DEG C, magnesium sulfite initial concentration 20g/L, pH7.0, forces the air mass flow 60L.h blasted
-1.The concentration of sulfate ion in solution is measured in different time points, conversion to obtain under different embodiment condition the time dependent relation of sulfate radical total amount in solution, known, acid ion is roughly linear growth along with the increase in reaction time, and the straight slope that now corresponding each embodiment obtains is the oxidizing reaction rate of magnesium sulfite under different catalysts action condition.
Experimental result shows, after adding catalyst, the oxidation rate of magnesium sulfite comparatively improves more than 50% without catalytic condition, and reacts due to accelerated oxidation the forward facilitating desulphurization reaction and carry out, thus desulfuration efficiency is necessarily promoted.
Claims (7)
1. for a solid phase composite metallic catalyst for magnesium processes sulfur removal technology, it is characterized in that, described catalyst is by water-soluble for the salt containing metal ion, and utilizes molybdate to make it co-precipitation, precipitation drying, oven dry, roasting is prepared from; The described salt containing metal ion is manganous salt, divalent cobalt, cupric salt, divalent nickel salt, trivalent iron salt and trivalent bismuth salt, and wherein the mass percent of metal ion manganese, cobalt, copper, bismuth, iron, nickel is: (1-5): (7-20): (2-10): (1-5): (2-10): 1.
2. solid phase composite metallic catalyst according to claim 1, it is characterized in that, in described catalyst, the mass percent of metal ion manganese, cobalt, copper, bismuth, iron, molybdenum, nickel is: (1-5): (7-20): (2-10): (1-5): (2-10): (14-60): 1.
3. solid phase composite metallic catalyst according to claim 1, it is characterized in that, described manganous salt, divalent cobalt, cupric salt, divalent nickel salt, trivalent iron salt and trivalent bismuth salt be respectively in sulfate, nitrate and chloride one or more.
4. solid phase composite metallic catalyst according to claim 1, is characterized in that, described molybdate is one or more in sodium salt, ammonium salt and sylvite.
5. solid phase composite metallic catalyst according to claim 1, is characterized in that, the condition of described drying is at 100 DEG C ~ 120 DEG C dry 8 ~ 12 hours.
6. solid phase composite metallic catalyst according to claim 1, is characterized in that, the condition of described oven dry is dry 9 ~ 12 hours at 200 DEG C ~ 300 DEG C.
7. solid phase composite metallic catalyst according to claim 1, is characterized in that, the condition of described last roasting is roasting 4 ~ 8 hours at 400 DEG C ~ 600 DEG C.
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| CN103977832B (en) * | 2014-04-28 | 2016-04-13 | 华北电力大学（保定） | A kind of for support type solid metallic Catalysts and its preparation method in magnesium processes sulfur removal technology |
| CN104492440B (en) * | 2015-01-12 | 2017-05-17 | 华北电力大学（保定） | Solid-phase catalyst for recovery of magnesium desulphurization byproducts and preparation method of solid-phase catalyst |
| JP6495470B2 (en) * | 2015-08-12 | 2019-04-03 | ノース チャイナ エレクトリック パワー ユニバーシティー パオティン | Multi-walled carbon nanotube catalyst, its production method and its use |
| CN107107040B (en) * | 2015-08-12 | 2020-02-07 | 华北电力大学（保定） | Supported solid-phase catalyst and preparation method and application thereof |
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| US20060199730A1 (en) * | 2005-03-02 | 2006-09-07 | Seely Michael J | Composition and method for improving density and hardness of fluid bed catalysts |
| KR100888133B1 (en) * | 2007-10-02 | 2009-03-13 | 에스케이에너지 주식회사 | Method of preparing multicomponent bismuth molybdate catalysts comprising four metal components and method of preparing 1,3-butadiene using said catalysts |
| CN101618331B (en) * | 2009-07-28 | 2012-02-08 | 清华大学 | Composite metallic catalyst for desulfurization by magnesium and preparation method thereof |
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