CN103285875A - 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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- CN103285875A CN103285875A CN201310248369XA CN201310248369A CN103285875A CN 103285875 A CN103285875 A CN 103285875A CN 201310248369X A CN201310248369X A CN 201310248369XA CN 201310248369 A CN201310248369 A CN 201310248369A CN 103285875 A CN103285875 A CN 103285875A
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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 the composite metallic catalyst preparing technical field, be specifically related to a kind of solid phase composite metallic catalyst for the oxidation of magnesium method sulfur removal technology accessory substance magnesium sulfite.Catalyst of the present invention is by improving the oxidizing reaction rate of magnesium sulfite, thereby solve desulphurization system because of the fouling of magnesium sulfite excessive concentration and blocking problem, and can effectively 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 that causes contamination phenomenon such as acid rain and grey haze, in recent years China's atmospheric environment caused significant damage.The desulfurization of magnesium method is present middle-size and small-size Industrial Boiler flue gas treating process commonly used, but because the oxidation reaction of accessory substance sulphite is slow relatively, cause investment and the energy consumption of desulfurizing byproduct recovery technology all higher, and the inadequate present situation of sulfite oxidation also easily cause system's fouling obstruction, low, the relief liquor secondary pollution problems of product quality.
Solving the hypodynamic main means of desulphurization system energy of oxidation at present is to add metal ion catalyst to improve the oxidation rate of magnesium sulfite.But because catalyst all adds desulfurization slurry with the solution form, cause the operating cost of application process higher, and catalyst is difficult to be reclaimed and will cause also and occur heavy metal secondary pollution phenomenon in desulfuration byproduct and the exterior liquid that therefore Application of Catalyst also is greatly limited.
Summary of the invention
The present invention has overcome the deficiency of existing liquid metal ionic catalyst, and a kind of solid phase composite metallic catalyst for magnesium method sulfur removal technology is provided.
A kind of solid phase composite metallic catalyst for magnesium method sulfur removal technology, described catalyst is that the salt that contains metal ion is water-soluble, and utilizes molybdate to make it co-precipitation, and precipitation drying, oven dry, roasting are prepared from; The described salt that contains 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.
The mass percent of metal ion manganese, cobalt, copper, bismuth, iron, molybdenum, nickel is in the described catalyst: (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 are respectively one or more in sulfate, nitrate and the chloride.
Described molybdate is one or more in sodium salt, ammonium salt and the sylvite.
The condition of described drying is following dry 8～12 hours at 100 ℃～120 ℃.
The condition of described oven dry is to dry 9～12 hours down at 200 ℃～300 ℃.
The condition of described last roasting is 400 ℃～600 ℃ following roastings 4～8 hours.
Catalyst preparation process of the present invention is simple, and is easy to operate.Compare with prior art, the present invention has following advantage: (1) solid-phase catalyst preparation manipulation of the present invention condition is simple.(2) solid catalysis effect of the present invention is more remarkable, and the oxidation rate of magnesium sulfite is improved more than 50%, can effectively be applied to the optimization of magnesia sulfur removal technology oxidative system.(3) use of the present invention can not cause negative effect to desulphurization system, also can react because of accelerated oxidation to promote the forward of desulphurization reaction to carry out, thereby improve desulfuration efficiency to a certain extent.(4) solid-phase catalyst consumption of the present invention is little, easily reclaims, and is residual few, can produce the secondary pollution problem hardly, also avoided the wasting of resources.
Description of drawings
Fig. 1 is solid-phase catalyst catalytic effect figure.
The specific embodiment
In order to be illustrated more clearly in the present invention, enumerate following examples, but it there is not any restriction to scope of the present invention.
The computational methods of rate of catalysis reaction:
Getting a certain amount of catalyst is added in the magnesium sulfite oxidation system, the concentration of sulfate radical in every certain interval of time assaying reaction device, represent the oxidizing reaction rate of magnesium sulfite can get the reaction rate of magnesium sulfite under catalytic condition with sulfate radical growing amount in the unit interval.
Embodiment 1
Take by weighing 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 the 20ml deionized water at ambient temperature, mixes successively, stirs, water bath method, 120
oDrying is 8 hours under the C condition, and 300
oOven dry is 9 hours under the C condition, and 520
oRoasting is 5 hours under the C condition, makes solid-phase catalyst.
Take by weighing above-mentioned catalyst 0.202g, add in the magnesium sulfite oxidation reactor, the reaction solution volume is 200ml, and rate of catalysis reaction did not have catalytic condition and improved about 0.570 times this moment.
Embodiment 2
Take by weighing 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 the 20ml deionized water at ambient temperature, mixes successively, stirs, water bath method, 120
oDrying is 8 hours under the C condition, and 300
oOven dry is 9 hours under the C condition, and 480
oRoasting is 5 hours under the C condition, makes solid-phase catalyst.
Take by weighing above-mentioned catalyst 0.202g, add in the magnesium sulfite oxidation reactor, the reaction solution volume is 200ml, and rate of catalysis reaction did not have catalytic condition and improved about 0.558 times this moment.
Embodiment 3
Take by weighing 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 the 20ml deionized water at ambient temperature, mixes successively, stirs, water bath method, 120
oDrying is 8 hours under the C condition, and 300
oOven dry is 9 hours under the C condition, and 500
oRoasting is 5 hours under the C condition, makes solid-phase catalyst.
Take by weighing above-mentioned catalyst 0.203g, add in the magnesium sulfite oxidation reactor, the reaction solution volume is 200ml, and rate of catalysis reaction did not have catalytic condition and improved about 0.566 times this moment.
Embodiment 4
Take by weighing 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 the 20ml deionized water at ambient temperature, mixes successively, stirs, water bath method, 100
oDrying is 12 hours under the C condition, and 200
oOven dry is 12 hours under the C condition, and 550
oRoasting is 5 hours under the C condition, makes solid-phase catalyst.
Take by weighing above-mentioned catalyst 0.201g, add in the magnesium sulfite oxidation reactor, the reaction solution volume is 200ml, and rate of catalysis reaction did not have catalytic condition and improved about 0.777 times this moment.
Embodiment 5
Take by weighing 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 the 20ml deionized water at ambient temperature, mixes successively, stirs, water bath method, 100
oDrying is 12 hours under the C condition, and 200
oOven dry is 12 hours under the C condition, and 450
oRoasting is 8 hours under the C condition, makes solid-phase catalyst.
Take by weighing above-mentioned catalyst 0.202g, add in the magnesium sulfite oxidation reactor, the reaction solution volume is 200ml, and rate of catalysis reaction did not have catalytic condition and improved about 1.698 times this moment.
The catalytic reaction effect of embodiment 1～5 is as shown in Figure 1: " case0 " represented the course of reaction of magnesium sulfite oxidation under the 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, and 35 ℃, magnesium sulfite initial concentration 20g/L, pH7.0 forces the air mass flow 60L.h that blasts
-1The concentration of sulfate ion in different time points mensuration solution, conversion obtains under the different embodiment conditions the time dependent relation of sulfate radical total amount in the solution, as can be known, acid ion is roughly linear growth along with the increase in reaction time, and the straight slope that this moment, corresponding each embodiment obtained is the oxidizing reaction rate of magnesium sulfite under the different catalysts action condition.
Experimental result shows that behind the adding catalyst, the oxidation rate of magnesium sulfite does not have catalytic condition and improved more than 50%, and because the accelerated oxidation reaction has promoted the forward of desulphurization reaction to carry out, thereby desulfuration efficiency is necessarily promoted.
Claims (7)
1. a solid phase composite metallic catalyst that is used for magnesium method sulfur removal technology is characterized in that described catalyst is that the salt that contains metal ion is water-soluble, and utilizes molybdate to make it co-precipitation, and precipitation drying, oven dry, roasting are prepared from; The described salt that contains 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 the mass percent of metal ion manganese, cobalt, copper, bismuth, iron, molybdenum, nickel is in the described catalyst: (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 are respectively one or more in sulfate, nitrate and the chloride.
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 the sylvite.
5. solid phase composite metallic catalyst according to claim 1 is characterized in that, the condition of described drying is following dry 8～12 hours at 100 ℃～120 ℃.
6. solid phase composite metallic catalyst according to claim 1 is characterized in that, the condition of described oven dry is to dry 9～12 hours down at 200 ℃～300 ℃.
7. solid phase composite metallic catalyst according to claim 1 is characterized in that, the condition of described last roasting is 400 ℃～600 ℃ following roastings 4～8 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977832A (en) * | 2014-04-28 | 2014-08-13 | 华北电力大学（保定） | Loaded solid phase metal catalyst for magnesium desulfurization process, and preparation method thereof |
| CN104492440A (en) * | 2015-01-12 | 2015-04-08 | 华北电力大学（保定） | Solid-phase catalyst for recovery of magnesium desulphurization byproducts and preparation method of solid-phase catalyst |
| CN107107038A (en) * | 2015-08-12 | 2017-08-29 | 华北电力大学（保定） | A kind of multiple-wall carbon nanotube catalyst and its preparation method and application |
| CN107107040A (en) * | 2015-08-12 | 2017-08-29 | 华北电力大学（保定） | A kind of loaded solid-phase catalyst and its preparation method and application |
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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 |
| CN101618331A (en) * | 2009-07-28 | 2010-01-06 | 清华大学 | Composite metallic catalyst for desulfurization by magnesium and preparation method thereof |
| CN101815578B (en) * | 2007-10-02 | 2013-01-02 | Sk新技术株式会社 | Method of preparing multicomponent bismuth molybdate catalysts comprising four metal components and method of preparing 1,3-butadiene using the catalysts |
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2013
- 2013-06-21 CN CN201310248369.XA patent/CN103285875B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN101815578B (en) * | 2007-10-02 | 2013-01-02 | Sk新技术株式会社 | Method of preparing multicomponent bismuth molybdate catalysts comprising four metal components and method of preparing 1,3-butadiene using the catalysts |
| CN101618331A (en) * | 2009-07-28 | 2010-01-06 | 清华大学 | Composite metallic catalyst for desulfurization by magnesium and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977832A (en) * | 2014-04-28 | 2014-08-13 | 华北电力大学（保定） | Loaded solid phase metal catalyst for magnesium desulfurization process, and preparation method thereof |
| CN104492440A (en) * | 2015-01-12 | 2015-04-08 | 华北电力大学（保定） | Solid-phase catalyst for recovery of magnesium desulphurization byproducts and preparation method of solid-phase catalyst |
| CN107107038A (en) * | 2015-08-12 | 2017-08-29 | 华北电力大学（保定） | A kind of multiple-wall carbon nanotube catalyst and its preparation method and application |
| CN107107040A (en) * | 2015-08-12 | 2017-08-29 | 华北电力大学（保定） | A kind of loaded solid-phase catalyst and its preparation method and application |
| US10434501B2 (en) * | 2015-08-12 | 2019-10-08 | North china electric power university baoding | Supported solid phase catalyst, and preparation method and use thereof |
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