CN107902699A - A kind of decomposition method of continuous pressure self-heating liquid phase oxidation chromite - Google Patents
A kind of decomposition method of continuous pressure self-heating liquid phase oxidation chromite Download PDFInfo
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Abstract
The present invention discloses a kind of decomposition method of continuous pressure self-heating liquid phase oxidation chromite, using chromite as raw material, using sodium hydroxide solution as reaction medium, after slurry mixing preheating, it is delivered in continuous pressure reaction kettle and is passed through oxidizing gas, control inlet amount and the balance of load, reaction kettle insulation continues reaction in kettle, after the completion of reaction, chromium acid sodium solution is obtained by separation of solid and liquid, washing, molten brilliant and removal of impurities etc..Present invention process is simple, flow is short, workable, it is easy to accomplish industrialized production.Meanwhile present invention process does not produce chromate waste water.Lye can be realized and recycled in system, environment friendly and pollution-free.
Description
Technical field
The present invention relates to chromium salt production field, it particularly relates to a kind of continuous pressure self-heating liquid phase oxidation chromite
Decomposition method.
Background technology
The yield of China's chromic salts has accounted for the 40% of the whole world.The total size increase of China's chromium salt factory, production capacity are also universal
Increase (the small factory less than 10,000 t/a has been eliminated, and the big factory more than 50,000 t/a is 2 existing).Existing chromite has calcium roasting
Process resource utilization rate is very low, and product per ton can produce 2.5~3 tons of the waste residue of carcinogenicity containing Cr6+ and other wastes containing chromium.Nothing
Calcium roasting technique is effectively reduced the pollution of chromium slag discharge, but produces product per ton and can still produce 0.8 ton of chromium residue and big
Chromium-containing waste gas is measured, the discarded object of discharge seriously jeopardizes environment and industry survival and development.
For traditional handicraft there are the problem of, substantial amounts of research concentrates on liquid phase oxidation processing chromite.Patent
In CN101659444, chromite is reacted in NaOH media system with oxidizing gas, while NaNO3 makes as catalyst
Chromium is sufficiently reacted in chromite.The product of hybrid reaction is lye and brilliant slag mixture, and brilliant slag dissolves, solid-liquor separation
Afterwards, chromium acid sodium solution is obtained, evaporative crystallization can obtain crystals of sodium chromate, after eluting to obtained crystals of sodium chromate and is dry, most
The sodium chromate product of qualification is obtained eventually.But due to the introducing of nitrate, the separation of crystalline mother solution and recycle more multiple
It is miscellaneous.Patent CN104341004 uses potassium hydroxide solution pressure leaching chromite, is passed through oxygen and is reacted, partial pressure of oxygen control
Slurry is diluted after 0.1~3.0MPa, reaction, and all dissolving enters liquid phase, liquid phase dilution and oxygenation to potassium chromate crystal
After calcium removal of impurities, potassium chromate crystal product that evaporative crystallization is purified.The technique chromium recovery ratio is conducive to chromic acid more than 95%
The separation of potassium and potassium hydroxide, but since raw material uses potassium hydroxide, process operation cost is higher.CN104512931A patents
In, after chromite is mixed with NaOH solution, oxidizing gas heating reaction is passed through, pulp dilution, separation of solid and liquid after reaction, remove
Crystals of sodium chromate and crystalline mother solution are obtained after miscellaneous, evaporative crystallization, crystals of sodium chromate obtains the chromic acid of qualification after elution and drying
Sodium product.Method process advan the efficiently separating in sodium chromate, but reaction process pressure is larger, equipment investment is higher.
The content of the invention
The main object of the present invention is：For chrominm salt production technology present situation, develop a kind of optimization, efficient, low energy consumption,
The decomposition chromium iron ore of low cost prepares the energy-saving and environment-friendly new method of sodium chromate.
To achieve the above object, the technical solution taken of the present invention is：
A kind of decomposition method of continuous pressure self-heating liquid phase oxidation chromite, it is characterised in that this method includes following
Step：
(1) chromite is mixed with sodium hydroxide solution, after being heated to 220~260 DEG C, is delivered to and is pre-heated to instead
Answer the continuous pressure reaction kettle of start-up temperature；
(2) pro-oxidant is added in continuous pressure reaction kettle, the mass ratio of pro-oxidant and chromite is：0.00001:
1~0.3:1, then pass to oxidizing gas and start to react, and kept the temperature, maintain reaction to continue by the heat release of reaction in kettle
Carrying out, the stringent partial pressure and gas flow for controlling oxidizing gas, partial pressure be 0.8~2.5MPa, gas flow is 0.5~
4.5m3/ h, makes reaction start rear temperature in the kettle and rises to 280~300 DEG C, adjust inlet amount and load in suitable scope
It is interior, and keep balancing；
Wherein, the continuous pressure reaction kettle is horizontal reacting kettle, and 3~5 chambers, each room are set in horizontal reacting kettle
Inside there are stirring and oxygen to be passed through pipeline, there is partition plate between room, slurry is delivered to bedroom reaction kettle, fully anti-in previous chamber
Overflow sequentially enters next chamber after answering, and enters flash vessel to after fully reacting；
(3) after the completion of reacting, slurry enters in flash vessel, and the high-temperature steam after flash distillation returns to chromite and sodium hydroxide mixes
The process of preheating is closed, slurry then enters the next step；
(4) slurry adds suitable aldehydes or alcohol compound after reacting, wherein, aldehydes or alcohol compound are with helping oxidation
Agent mass ratio is 0.1:1~3:1, make pro-oxidant generation precipitation, slurry separation of solid and liquid obtains filtrate and filter cake, and filtrate returns
Mixed with chromite, for filter cake after washing, molten brilliant and removal of impurities, separation of solid and liquid, obtains scum and chromium acid sodium solution.
Technical solution may further be：The mass ratio of sodium hydroxide solution and chromite is 2 in the step (1):1~
10:1。
Technical solution may further be：Pro-oxidant described in the step (2) for sodium manganate, potassium manganate, potassium permanganate,
One or more of mixtures in sodium permanganate.
Technical solution may further be：Oxidizing gas described in the step (2) is air, oxygen, ozone are therein
One or several kinds of mixtures.
Technical solution may further be：Aldehydes or alcohol compound are formaldehyde, acetaldehyde, propionic aldehyde, fourth in the step (4)
Aldehyde, valeral, methanol, ethanol, propyl alcohol, butanol, amylalcohol one or several kinds of mixture therein.
Technical solution may further be：The filtrate in the step (4) is containing Na2CrO4, NaOH and sodium aluminate, silicon
The solution of the impurity such as sour sodium, its component are：Na2CrO4：1~15wt%；NaOH：20~70wt%；Al2O3：0.1~5wt%；
SiO2：0.1~5wt%.
Technical solution may further be：The filter cake in the step (4) is containing crystal and scum and helps oxygen on a small quantity
The sodium chromate crystalline substance slag of agent sediment, its component are：Na2CrO4：5~50wt%；NaOH：20~60wt%, pro-oxidant sink
Starch：0.00002~0.6wt%.
Technical solution may further be：The component of chromium acid sodium solution is in the step (4)：NaOH：1~10wt%,
Na2CrO4：1~50wt%.
In conclusion the chromite continuous pressure self-heating liquid phase oxidation that the present invention proposes a kind of optimization prepares sodium chromate
New method, the characteristics of making full use of exothermic heat of reaction, be passed through the oxidizing gas of relatively low partial pressure, controls inlet amount and load
Balance, makes reaction kettle keep the temperature and be reacted in kettle and continues, and realizes continuous pressure certainly in the successive reaction kettle of specific structure
The effect of hot type, the high-temperature steam after flashing can return to preheating procedure, make full use of and improve energy utilization rate, have into
The environment-friendly advantage that this is low, energy consumption is low.It is workable, it is easy to accomplish industrial metaplasia meanwhile present invention process is simple, flow is short
Production.Meanwhile after the completion of present invention reaction, chromium acid sodium solution is obtained by separation of solid and liquid, washing, molten brilliant and removal of impurities etc., technique is not
Produce chromate waste water.Lye can be realized and recycled in system, environment friendly and pollution-free.Therefore, not only had using the technique of the present invention
There is significant economic benefit, and meet environmental requirement, be an effective way of chromic salts enterprise production.
Brief description of the drawings
Attached drawing described herein is used for providing further understanding the embodiment of the present invention, forms one of the present invention
Point, do not form the restriction to the embodiment of the present invention.
Fig. 1 is the process flow diagram of the present invention.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiment and attached drawing, to this
Invention is described in further detail, and exemplary embodiment of the invention and its explanation are only used for explaining the present invention, do not make
For limitation of the invention.
Embodiment 1.
According to NaOH/ chromite=3:1 is uniformly mixed 70wt% lye with chromite, mixed material heating to 290 DEG C simultaneously
It is delivered to continuous pressure reaction kettle.According to pro-oxidant：Chromite=0.005:1 adds potassium permanganate, is passed through ozone and carries out instead
Should, partial pressure 0.8MPa, gas flow 4.2m3/h.Reaction kettle insulation makes reaction in kettle persistently be carried out by self-heating, same to time control
The balance of inlet amount processed and load.Enter flash vessel after the completion of reaction, the high-temperature steam after flash distillation returns to chromite and lye
Preheating procedure is mixed, slurry adds formaldehyde and carries out separation of solid and liquid, and filtrate returns and mixed with chromite, sodium chromate crystalline substance slag (chromic acid
Sodium 35wt%, sodium hydroxide 55wt%) carry out washing and molten crystalline substance.Chromium acid sodium solution component after molten crystalline substance：Sodium hydroxide 10wt%, chromium
Sour sodium 45wt%.In chromite liquid-phase oxidation process, the Oxidation Leaching rate 99.8% of chromium.
Embodiment 2.
According to NaOH/ chromite=8:1 is uniformly mixed 35wt% lye with chromite, mixed material heating to 220 DEG C simultaneously
It is delivered to continuous pressure reaction kettle.According to pro-oxidant：Chromite=0.01:1 adds sodium permanganate, is passed through oxygen and air mixes
Compound is reacted, partial pressure 1.8MPa, gas flow 0.8m3/h.Reaction kettle insulation makes reaction in kettle continue by self-heating
Carry out, while control inlet amount and the balance of load.Enter flash vessel after the completion of reaction, the high-temperature steam after flash distillation returns to chromium
Iron ore and lye mixing preheating procedure, slurry add butanol and carry out separation of solid and liquid, and filtrate returns and mixed with chromite, solid
(sodium chromate 15wt%, sodium hydroxide 35wt%) carries out washing and molten crystalline substance.Chromium acid sodium solution component after molten crystalline substance：Sodium hydroxide
7wt%, sodium chromate 30wt%.In chromite liquid-phase oxidation process, the Oxidation Leaching rate 99.6% of chromium.
Embodiment 3.
According to NaOH/ chromite=6:1 is uniformly mixed 55wt% lye with chromite, mixed material heating to 250 DEG C simultaneously
It is delivered to continuous pressure reaction kettle.According to pro-oxidant：Chromite=0.2:1 adds sodium manganate, is passed through oxygen and is reacted, point
Press as 1.3MPa, gas flow 3.2m3/h.Reaction kettle insulation makes reaction in kettle persistently be carried out by self-heating, at the same control into
The balance of doses and load.Enter flash vessel after reaction, the high-temperature steam after flash distillation returns to chromite and lye mixing
Preheating procedure, slurry add valeral and carry out separation of solid and liquid, and filtrate returns and mixed with chromite, solid (sodium chromate 25wt%, hydrogen
Sodium oxide molybdena 45wt%) carry out washing and molten crystalline substance.Chromium acid sodium solution component after molten crystalline substance：Sodium hydroxide 4wt%, sodium chromate 15wt%.
In chromite liquid-phase oxidation process, the Oxidation Leaching rate 99.5% of chromium.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention god.
Claims (8)
1. a kind of decomposition method of continuous pressure self-heating liquid phase oxidation chromite, it is characterised in that this method includes following step
Suddenly：
(1) chromite is mixed with sodium hydroxide solution, after being heated to 220~260 DEG C, is delivered to and is pre-heated to reaction and opens
The continuous pressure reaction kettle of dynamic temperature；
(2) pro-oxidant is added in the continuous pressure reaction kettle, the mass ratio of pro-oxidant and chromite is：0.00001:
1~0.3:1, then pass to oxidizing gas and start to react, and kept the temperature, maintain reaction to continue by the heat release of reaction in kettle
Carrying out, the stringent partial pressure and gas flow for controlling oxidizing gas, partial pressure be 0.8~2.0MPa, gas flow is 0.5~
4.5m3/ h, makes reaction start rear temperature in the kettle and rises to 280~300 DEG C, adjust inlet amount and load in suitable scope
It is interior, and keep balancing；
Wherein, the continuous pressure reaction kettle is horizontal reacting kettle, and 3~5 chambers are set in horizontal reacting kettle, each indoor equal
There are stirring and oxygen to be passed through pipeline, there is partition plate between room, slurry is delivered to bedroom reaction kettle, after fully being reacted in previous chamber
Overflow sequentially enters next chamber, enters flash vessel to after fully reacting；
(3) after the completion of reacting, slurry enters in flash vessel, and the high-temperature steam after flash distillation returns to chromite and sodium hydroxide mixing is pre-
The process of heat, slurry then enter the next step；
(4) slurry adds suitable aldehydes or alcohol compound after reacting, wherein, aldehydes or alcohol compound and pro-oxidant matter
Amount is than being 0.1:1~3:1, make pro-oxidant generation precipitation, slurry separation of solid and liquid, obtains filtrate and filter cake, and filtrate returns and chromium
Iron ore mixes, and filter cake is after washing, molten brilliant and removal of impurities, then separation of solid and liquid, obtains scum and chromium acid sodium solution.
2. according to the method described in claim 1, it is characterized in that：Sodium hydroxide solution and chromite in the step (1)
Mass ratio is 2:1~10:1.
3. according to the method described in claim 1, it is characterized in that：Pro-oxidant described in the step (2) is sodium manganate, manganese
One or more of mixtures in sour potassium, potassium permanganate, sodium permanganate.
4. according to the method described in claim 1, it is characterized in that：Oxidizing gas described in the step (2) is air, oxygen
Gas, ozone one or several kinds of mixture therein.
5. according to the method described in claim 1, it is characterized in that：In the step (4) aldehydes or alcohol compound be formaldehyde,
Acetaldehyde, propionic aldehyde, butyraldehyde, valeral, methanol, ethanol, propyl alcohol, butanol, amylalcohol one or several kinds of mixture therein.
6. according to the method described in claim 6, it is characterized in that：The filtrate in the step (4) is containing Na2CrO4、
The solution of the impurity such as NaOH and sodium aluminate, sodium metasilicate, its component are：Na2CrO4：1~15wt%；NaOH：20~70wt%；
Al2O3：0.1~5wt%；SiO2：0.1~5wt%.
7. according to the method described in claim 1, it is characterized in that：The filter cake in the step (4) is containing crystal and iron
The sodium chromate crystalline substance slag of slag and a small amount of pro-oxidant sediment, its component are：Na2CrO4：5~50wt%；NaOH：20~
60wt%, pro-oxidant sediment：0.00002~0.6wt%.
8. according to the method described in claim 1, it is characterized in that：The component of chromium acid sodium solution is in the step (4)：
NaOH：1~10wt%, Na2CrO4：1~50wt%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196972A (en) * | 2021-12-21 | 2022-03-18 | 青海省博鸿化工科技股份有限公司 | Production system and method for preparing chromium oxide green and co-producing sodium dichromate |
| CN114195189A (en) * | 2021-12-21 | 2022-03-18 | 青海省博鸿化工科技股份有限公司 | Preparation process of hydroxyl chromic oxide |
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| CN101817561A (en) * | 2010-04-12 | 2010-09-01 | 中国科学院过程工程研究所 | Method for pollution-free production of sodium chromate by pressure leaching of chromite |
| CN103086433A (en) * | 2013-03-11 | 2013-05-08 | 湖北振华化学股份有限公司 | Method for preparing sodium dichromate by sodium-based molten salt oxidation continuous carbonization |
| CN104726689A (en) * | 2013-12-24 | 2015-06-24 | 中国科学院过程工程研究所 | Method for decomposing chromite by low-temperature atmospheric-pressure fluidization |
| CN106186068A (en) * | 2016-07-06 | 2016-12-07 | 于广新 | The clean preparation method of chromate is prepared in a kind of Continuous Liquid Phase oxidation |
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- 2017-11-14 CN CN201711124444.6A patent/CN107902699B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817561A (en) * | 2010-04-12 | 2010-09-01 | 中国科学院过程工程研究所 | Method for pollution-free production of sodium chromate by pressure leaching of chromite |
| CN103086433A (en) * | 2013-03-11 | 2013-05-08 | 湖北振华化学股份有限公司 | Method for preparing sodium dichromate by sodium-based molten salt oxidation continuous carbonization |
| CN104726689A (en) * | 2013-12-24 | 2015-06-24 | 中国科学院过程工程研究所 | Method for decomposing chromite by low-temperature atmospheric-pressure fluidization |
| CN106186068A (en) * | 2016-07-06 | 2016-12-07 | 于广新 | The clean preparation method of chromate is prepared in a kind of Continuous Liquid Phase oxidation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196972A (en) * | 2021-12-21 | 2022-03-18 | 青海省博鸿化工科技股份有限公司 | Production system and method for preparing chromium oxide green and co-producing sodium dichromate |
| CN114195189A (en) * | 2021-12-21 | 2022-03-18 | 青海省博鸿化工科技股份有限公司 | Preparation process of hydroxyl chromic oxide |
| CN114196972B (en) * | 2021-12-21 | 2023-11-10 | 青海省博鸿化工科技股份有限公司 | Production system and method for preparing chromium oxide green and co-producing sodium dichromate |
| CN114195189B (en) * | 2021-12-21 | 2024-01-02 | 青海省博鸿化工科技股份有限公司 | Preparation process of chromium oxyhydroxide |
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