CN107601547A - The control method of remaining chlorinity in metal oxide - Google Patents
The control method of remaining chlorinity in metal oxide Download PDFInfo
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- CN107601547A CN107601547A CN201710751527.1A CN201710751527A CN107601547A CN 107601547 A CN107601547 A CN 107601547A CN 201710751527 A CN201710751527 A CN 201710751527A CN 107601547 A CN107601547 A CN 107601547A
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- metal oxide
- gas
- chlorinity
- control method
- heat treatment
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Abstract
The invention provides a kind of control method of remaining chlorinity in metal oxide, comprise the following steps：S1：Prepare vapor and deliver the gaseous mixture of gas, delivery gas is passed through steam generator, the steam evaporator is dispersed into bubble by gas is delivered, bubble fully contacts with vapor, obtain the delivery air water steam mixed gas of water partial pressure saturation, the steam evaporator temperature is controlled, adjusts water vapour content in the mixed gas；S2：Low Temperature Heat Treatment, mixed gas described in S1 is passed through in the dechlorination heat treatment reactor of chloride metal oxide, and heat treatment reaction atmosphere is used as using it, based on thermodynamical equilibrium reaction conversions relation between metal oxide and metal chloride, adjusted by water vapour content in mixed gas described in S1, control the residual chlorinity in metal oxide.The metal-oxide powder material chlorinity for handling to obtain by the method for the invention is low, and does not destroy the pattern and structure of material.
Description
Technical field
The present invention relates to metal-oxide powder field of material preparation, and in particular to residual chlorine contains in a kind of metal oxide
The control method of amount.
Background technology
Metal oxide has extensive use in fields such as electrode material, catalyst, capacitor materials.With application
Continuous expansion, requirement to material physicochemical property itself also more and more higher.Therefore the stage that must be prepared to powder body material enters
How the strict control of row, prepare uniform component, the metal oxide materials of function admirable become focus of concern.Mesh
The preceding method for preparing metal oxide and raw material have many kinds, when using metal chloride as raw material, pyrolysis prepares metal oxidation
During powder material, due to HCl tail gas caused by thermal decomposition easily and product generation secondary response (such as：NiO+2HCl (g)=
NiCl2+H2O(g)；2Co3O4+ 12HCl (g)=6CoCl2+6H2O(g)+O2(g)；2MnO2+ 4HCl (g)=2MnCl2+2H2O(g)
+O2(g) etc.), or chloride decomposition is not exclusively, can usually cause product higher chlorine element residual quantity to be present.Residual chlorinity
High and chloride itself water sorption, can bring serious adverse effect to the performance of material.
At present, in order to reduce residual chlorinity in oxide, simple and easy oxidizing roasting method can on the one hand be used.Such as
The author that [Central South University's journal, 2011,8,2215-2220] is reported is with CoCl2The aqueous solution has been prepared as raw material to be contained
Oxychloride, after it is subjected to oxidizing roasting processing at 800 DEG C, the height that residual chlorinity is less than 0.1% has finally been prepared
Purity Co3O4Powder.Although this method can effectively control residual chlorinity, but need higher equipment investment and high
Energy cost, it is most important that high temperature can destroy material self structure, influence material property.On the other hand, such as Publication No.
CN201610195086.7 discloses one kind by improving temperature of gathering dust, so as to reduce the method for residual chlorinity.This method can be
The effect for reaching on the basis of technological process and controlling residual chlorinity is not increased.But operating temperature is difficult to find that in actual production
Dust collection device more than 300 DEG C, and maintain bulky dust-precipitator to consume mass energy in higher operating temperature,
Cost is high.
A kind of method that energy consumption is low, investment is small and does not destroy the reduction chlorinity of material structure is studied, for preparing high property
Oxide and its application field important in inhibiting can be expanded.And how to control and reduce the oxygen prepared using chloride as raw material
Chlorinity in compound, it is still a problem.
The content of the invention
In order to solve problems of the prior art, the present invention provides a kind of energy consumption based on thermodynamic equilibrium theory
Method that is low, investing chlorinity in the good reduction metal oxide of small, efficiency high, adaptability.Handle what is obtained by the method
Metal-oxide powder material chlorinity is low, and will not destroy the pattern and structure of material, can be applied to various metals oxygen
Compound.Technical scheme proposed by the present invention comprises the following steps：
S1：Prepare delivery air-water steam mixed gas
The delivery gas (known mass flow) is passed through steam generator, the steam evaporator is dispersed into gas is delivered
Bubble, bubble fully contact with vapor, obtain the delivery air-water steam mixed gas of water partial pressure saturation；The water is controlled to steam
Gas generator temperature can adjust the partial pressure of vapor, so as to adjust water vapour content in the mixed gas；
S2：Low Temperature Heat Treatment
By the mixed gas described in S1 be passed through chloride metal oxide dechlorination heat treatment reactor in, and using its as
Reaction atmosphere is heat-treated, based on thermodynamical equilibrium reaction conversions relation between metal oxide and metal chloride, by S1
Water vapour content is adjusted in the mixed gas, controls the residual chlorinity in metal oxide.
Further, as a kind of preferred scheme, caused high-temperature tail gas is passed through to the vapor and occurred in the S2
In device, preheat the steam evaporator using waste heat from tail gas and absorb HCl.
Further, as a kind of preferred scheme, the steam generator is the core in water bath with thermostatic control or oil bath pan
Piece saturated steam generator.
Further, as a kind of preferred scheme, the metal ion of the metal chloride is Ni, Co, Mn, one in Fe
Kind is several；The method of metal chlorination preparing metal-oxide includes but is not limited to spray pyrolysis, is spray-dried, melts salt in S2
Pyrolysis, solid phase pyrolysis, microwave-heating.
Further, as a kind of preferred scheme, it is in compressed air, oxygen, nitrogen, argon gas that gas is delivered described in S1
It is one or more of；The delivery gas air velocity is 1-10L/min.
Further, as a kind of preferred scheme, the vapour content in the mixed gas is (in terms of mass fraction)
0-10%, preferably 0.5-5%.
Further, as a kind of preferred scheme, solution is housed described in S1 in steam evaporator, the solution is water
Or sodium hydrate aqueous solution, the concentration of sodium hydroxide is 0.1-2mol/L in the sodium hydrate aqueous solution.
Further, as a kind of preferred scheme, the operating temperature of steam generator described in S1 is 60-100 DEG C.
Further, as a kind of preferred scheme, heat treatment temperature is 200- in the heat treatment reactor of dechlorination described in S2
500 DEG C, heat treatment time 0.5-5h.
Further, chlorine element in the metal oxide being prepared as a kind of preferred scheme, the control method
Mass fraction is 0.01~2%.
The present invention has the advantages that：
The residual chlorinity of metal oxide is reduced compared to common high temperature oxidation roasting method, the present invention utilizes metal oxide
Thermodynamical equilibrium transformational relation between metal chloride, with the mixed gas of containing water vapor and delivery gas to containing oxychloride
Low Temperature Heat Treatment is carried out, dechlorination reaction is occurred at a lower temperature, high-purity mangesium oxide powder material is prepared.From
And other processing methods such as washing, high temperature are avoided to the destruction caused by powder body material structure；Meanwhile tail gas leads to after heat treatment
Enter steam evaporator, preheat steam evaporator, energy-conservation and the purpose of environmental protection can be achieved；This method is simple to operate, energy consumption into
This is low, and efficiency high, environmental pollution is small, and adaptability is good, and material physicochemical property will not be negatively affected.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, it will use below required in embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are some embodiments of the present invention, general for this area
For logical technical staff, on the premise of not paying creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
Accompanying drawing 1 is the XRD spectra comparison diagram of sample and No. 1 No. 4 samples before being heat-treated in embodiment 1 of the present invention.
Accompanying drawing 2 is the EDX spectrogram comparison diagrams of sample and No. 1 No. 4 samples before being heat-treated in embodiment 1 of the present invention.
Accompanying drawing 3 is the SEM comparison diagrams of sample and No. 1 No. 4 samples before being heat-treated in embodiment 1 of the present invention.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from known method.
Embodiment 1：
It is the nickel oxide powder body material of 9.92% (mass fraction) as reaction mass using residual chlorine prepared by spray pyrolysis, with
N2As the delivery gas of vapor, air velocity 5L/min, steam evaporator solution is water, and operating temperature is 60 DEG C；In gas
In the case that flow velocity degree and generator parameter are constant, make powder under 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C of different temperatures point
Not carry out 0.5h, 1.5h, 3h, 5h heat treatment, carry out SEM, XRD, EDX sign respectively to the material after heat treatment, and calculate
Except dechlorination rate.After waste heat from tail gas after heat treatment is absorbed by generator, steam evaporator is without additionally heating.
The experiment condition and result of the example 1 of table 1
Resulting material after the material heat treatment 3h that Fig. 1 is initial reactant (0# materials) and numbering is 1 and numbering is 4
XRD spectrum.It can be found that initial reactant and No. 1 material have the impurity peaks of chloride, phase in low-angle in XRD spectrum
No. 4 materials are wholly absent through Overheating Treatment impurity peaks than under.This explanation is with the rise of heat treatment temperature, the removing of chlorine element
Effect is more preferable.
By carrying out EDS signs respectively to above-mentioned three kinds of materials, as a result as shown in Figure 2.The result shows that No. 1 material exists
Being heat-treated residual chlorinity by 3h at 250 DEG C still has 8.79%, and residual dechlorination rate is only 11.4%；By contrast, No. 4 materials
Residual chlorinity is 1.05% after 3h is heat-treated at 400 DEG C, and residual dechlorination rate is 89.4%, is demonstrated again that with heat treatment temperature
Rise, the removal effect of chlorine element is more preferable.
From figure 3, it can be seen that two kinds of materials through Overheating Treatment have with the material before reaction as pattern, explanation
The method of the present invention reduction residual chlorinity of metal oxide will not destroy the existing appearance structure of raw material.
In order to systematically study the influence of heat treatment temperature and heat treatment time to residual dechlorination rate, embodiment and implementation
As a result it is as shown in table 1.As shown in Table 1, with the extension of heat treatment time and the removal efficiency for raising residual chlorine of heat treatment temperature
It will gradually rise.It is worth noting that, the residual dechlorination rate of the material of numbering 2 has greatly improved compared with the material of numbering 1, this
It is because oxide and the generation temperature of chloride counter reaction only have partial oxidation thing between 250 DEG C -300 DEG C at 250 DEG C
Converted, and nearly all chloride is converted for oxide at 300 DEG C.
Embodiment 2：
Cobaltosic oxide powder material of the residual chlorine prepared using spray pyrolysis as 3.30% (mass fraction) is used as reactant
Material, with N2、O2Delivery gas with Ar respectively as vapor, air velocity are respectively 2L/min, 5L/min, 10L/min, and water steams
Gas generator solution is sodium hydrate aqueous solution, and operating temperature is 90 DEG C, 300 DEG C of heat treatment reactor operating temperature, heat treatment
Time is 3h, carries out EDX signs respectively to the material after heat treatment, and calculate and remove dechlorination rate.Waste heat from tail gas after heat treatment
After being absorbed by generator, steam evaporator energy-conservation 60%.
The experiment condition and result of the example 2 of table 2
From the embodiment and result of implementation of table 2, the species for delivering gas and the uninterrupted for delivering gas also influence whether
The abjection effect of residual chlorine.When using three kinds of oxygen, argon gas, nitrogen gases as during delivery, wherein oxygen is as the residual chlorine for delivering gas
It is best to deviate from effect.With the increase of throughput, residual dechlorination rate reduces.
Embodiment 3：
Nickel oxide (chlorine element mass ratio is 5.24%), cobaltosic oxide similar in the residual chlorinity prepared using spray pyrolysis
(chlorine element mass ratio is 4.78%), manganese oxide (chlorine element mass ratio is 5.06%) powder body material are as reaction mass.With N2
As the delivery gas of vapor, air velocity 5L/min, steam evaporator solution is sodium hydrate aqueous solution (sodium hydroxide water
Naoh concentration is 1mol/L in solution), operating temperature is respectively 30 DEG C, 50 DEG C, 70 DEG C, 100 DEG C.In air velocity and hair
In the case of raw device parameter constant, powder is carried out 3h time heat treatments at 300 DEG C, the material after heat treatment is carried out respectively
EDX is characterized, and is calculated and removed dechlorination rate.After waste heat from tail gas after heat treatment is absorbed by generator, steam evaporator energy-conservation is aobvious
Write.
The experiment condition and result of the example 3 of table 3
From the embodiment and result of implementation of table 3, different (the i.e. gaseous mixture reclaimed water steamings of operating temperature of steam evaporator
Vapour partial pressure is different), residual chlorine removal effect is different, and residual dechlorination rate improves as generator operating temperature increases.Identical water
Under partial vapour pressure, mutually synthermal, same time heat treatment, different metal oxides are carried out to dissimilar metals oxide
Residual chlorine removal effect is different, this be due to balanced reaction temp between different metal oxides and chloride it is different caused by.
Embodiment 4：
The nickel oxide powder that residual chlorinity is respectively 21.31%, 12.25%, 7.83%, 4.26% is prepared with spray pyrolysis
Material is as reaction mass.With N2As the delivery gas of vapor, air velocity 5L/min, steam evaporator solution is water-soluble
Liquid, steam evaporator temperature is adjusted, it is respectively 1%, 3%, 5%, 10% (quality point to control water vapour content in gaseous mixture
Number).Powder is carried out 3h time heat treatments at 350 DEG C, carry out EDX signs respectively to the material after heat treatment, and calculate and remove
Dechlorination rate.After waste heat from tail gas after heat treatment is absorbed by generator, steam evaporator obvious energy conservation.
The experiment condition and result of the example 4 of table 4
In order to further analyze different water vapour contents to balanced reaction between metal oxide and metal chloride
Influence, the content of the vapor in gaseous mixture is accurately controlled in example 4, and measure in different water vapour contents
Under the conditions of, the residual chlorine removal effect of material after identical heat treatment temperature, identical heat treatment time.By the embodiment and reality of table 4
Apply result and understand that residual dechlorination rate increases with the increase of water vapour content.In addition, under the conditions of identical water vapour content,
The higher material of residual chlorinity, its residual chlorine removal effect are more preferable.
Although above the present invention is made to retouch in detail with general explanation, embodiment and experiment
State, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, are belonged to claimed
Scope.
Claims (10)
1. the control method of remaining chlorinity in a kind of metal oxide, it is characterised in that comprise the following steps：
S1：Prepare delivery air-water steam mixed gas
The delivery gas is passed through steam generator, the steam evaporator is dispersed into bubble, bubble and water by gas is delivered
Steam fully contacts, and obtains the delivery air-water steam mixed gas of water partial pressure saturation；The steam evaporator temperature is controlled,
Adjust water vapour content in the mixed gas；
S2：Low Temperature Heat Treatment
Mixed gas described in S1 is passed through in the dechlorination heat treatment reactor of chloride metal oxide, and using it as at hot
Reaction atmosphere is managed, based on thermodynamical equilibrium reaction conversions relation between metal oxide and metal chloride, described in S1
Water vapour content is adjusted in mixed gas, controls the residual chlorinity in metal oxide.
2. the control method of remaining chlorinity in metal oxide according to claim 1, it is characterised in that：In the S2
Caused high-temperature tail gas is passed through into the steam evaporator, and the steam evaporator is preheated using waste heat from tail gas.
3. the control method of remaining chlorinity in metal oxide according to claim 1, it is characterised in that：The water steams
Vapour generator is the core piece saturated steam generator in water bath with thermostatic control or oil bath pan.
4. the control method of remaining chlorinity in metal oxide according to claim 1, it is characterised in that：Described in S1
Delivery gas is the one or more in compressed air, oxygen, nitrogen, argon gas.
5. the control method of remaining chlorinity in the metal oxide described in claim 4, it is characterised in that：The delivery gas gas
Flow velocity degree is 1-10L/min.
6. the control method of remaining chlorinity in metal oxide according to claim 1, it is characterised in that：The mixing
Vapour content in gas（In terms of mass fraction）For 0-10%, preferably 0.5-5%.
7. the control method of remaining chlorinity in metal oxide according to claim 1, it is characterised in that：Described in S1
Solution is housed, the solution is water or sodium hydrate aqueous solution, hydrogen in the sodium hydrate aqueous solution in steam evaporator
The concentration of sodium oxide molybdena is 0.1-2mol/L.
8. the control method of remaining chlorinity in metal oxide according to claim 1, it is characterised in that：Described in S1
The operating temperature of steam generator is 60-100 DEG C.
9. the control method of remaining chlorinity in metal oxide according to claim 1, it is characterised in that：Described in S2
Heat treatment temperature is 200-500 DEG C in dechlorination heat treatment reactor, heat treatment time 0.5-5h.
10. the control method of remaining chlorinity in metal oxide according to claim 1, it is characterised in that：The control
The mass fraction of chlorine element is 0.01 ~ 2% in the metal oxide that method processed is prepared.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109052484A (en) * | 2018-10-25 | 2018-12-21 | 唐山学院 | Brown iron oxide dechlorination device and its control method |
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| RU2042628C1 (en) * | 1993-06-29 | 1995-08-27 | Нина Николаевна Стремилова | Method for dechlorination of titanium dioxide |
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| CN103320623A (en) * | 2013-07-08 | 2013-09-25 | 昆明理工大学 | Method and device for zinc oxide smoke dust dechlorinating by water vapor activating/microwave roasting |
| CN203346452U (en) * | 2013-07-08 | 2013-12-18 | 昆明理工大学 | Device for dechlorination of zinc oxide fume through steam activation/microwave roasting |
| CN104324928A (en) * | 2014-10-10 | 2015-02-04 | 昆明理工大学 | Extraction dechlorination method for zinc-hydrometallurgy CuCl slag through water vapor-oxygen enhanced microwave treatment |
| CN105692722A (en) * | 2016-03-31 | 2016-06-22 | 中南大学 | Method for lowering chlorine content in oxide preparation process by metal chloride spray pyrolysis |
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2017
- 2017-08-28 CN CN201710751527.1A patent/CN107601547A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2042628C1 (en) * | 1993-06-29 | 1995-08-27 | Нина Николаевна Стремилова | Method for dechlorination of titanium dioxide |
| CN102603013A (en) * | 2012-03-20 | 2012-07-25 | 湖北全阳磁性材料制造有限公司 | Novel method for dechlorinating acid-washing iron oxide red |
| CN103320623A (en) * | 2013-07-08 | 2013-09-25 | 昆明理工大学 | Method and device for zinc oxide smoke dust dechlorinating by water vapor activating/microwave roasting |
| CN203346452U (en) * | 2013-07-08 | 2013-12-18 | 昆明理工大学 | Device for dechlorination of zinc oxide fume through steam activation/microwave roasting |
| CN104324928A (en) * | 2014-10-10 | 2015-02-04 | 昆明理工大学 | Extraction dechlorination method for zinc-hydrometallurgy CuCl slag through water vapor-oxygen enhanced microwave treatment |
| CN105692722A (en) * | 2016-03-31 | 2016-06-22 | 中南大学 | Method for lowering chlorine content in oxide preparation process by metal chloride spray pyrolysis |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109052484A (en) * | 2018-10-25 | 2018-12-21 | 唐山学院 | Brown iron oxide dechlorination device and its control method |
| CN109052484B (en) * | 2018-10-25 | 2024-02-23 | 唐山学院 | Iron oxide powder dechlorination device and control method thereof |
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