CN103803495A - Treatment method for liquid waste produced during the acid-process preparation of aluminum oxide - Google Patents
Treatment method for liquid waste produced during the acid-process preparation of aluminum oxide Download PDFInfo
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- CN103803495A CN103803495A CN201310746760.2A CN201310746760A CN103803495A CN 103803495 A CN103803495 A CN 103803495A CN 201310746760 A CN201310746760 A CN 201310746760A CN 103803495 A CN103803495 A CN 103803495A
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- acid
- iron ore
- sour gas
- powdered iron
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Abstract
The invention discloses a treatment method for liquid waste produced during acid-process preparation of aluminum oxide. The treatment method comprises the following steps: S1, carrying out spray roasting on the liquid waste to obtain a first acidic gas and primary iron ore powder; and S2, recovering the first acidic gas and purifying the primary iron ore powder. According to the technical scheme disclosed by the invention, firstly, the liquid waste is subjected to spray roasted, so as to obtain the first acidic gas and the primary iron ore powder; the first acidic gas is recovered and the primary iron ore powder is purified, so that the acid in the liquid waste is recycled by recovery of the acidic gas. Iron and aluminum ions in the liquid waste are recovered by purification of the primary iron ore powder. Thus, the treatment method can be made into industrial products, resource utilization is maximized, and secondary pollutants are hardly generated.
Description
Technical field
The present invention relates to liquid waste disposal technique field, produce the treatment process of the waste liquid of aluminum oxide generation in particular to a kind of acid system.
Background technology
" a step acid pasting " produces alumina technology technology from flyash is that limited-liability company of Chinese Shenhua is through researching and developing for many years a kind of alumina technology method of producing that is different from bayer's process of invention.Produce in alumina technology process at acid system, owing to having produced in production line material scavenging process containing higher concentration FeCl
3and AlCl
3acid waste liquid give whole engineering of water treatment bring great difficulty.Traditional acid waste liquid treatment process has the alkali of adding neutralization, evaporate to dryness to store up, build the treatment processs such as evaporation pond nature evaporate to dryness and powder mix coal ash landfill, all there are in various degree some problems in these treatment processs, in as high in processing costs, treating processes, can produce secondary pollution, have follow-up potential safety hazard, waste ample resources etc., the problem that therefore can not fundamentally solve acid system and produce industrial wastewater.
Summary of the invention
The treatment process that the present invention aims to provide a kind of acid system and produces the waste liquid that aluminum oxide produces, to provide a kind of economy, environmental protection and can realize the method for utilization of wastewater resource.
To achieve these goals, according to an aspect of the present invention, provide a kind of acid system to produce the treatment process of the waste liquid of aluminum oxide generation.This treatment process comprises the following steps: S1, waste liquid is carried out to spray roasting, and obtain the first sour gas and elementary powdered iron ore; And S2, the first sour gas is reclaimed to the elementary powdered iron ore of purifying treatment.
Further, to the first sour gas reclaim comprise the first sour gas is contacted with absorption solution of acid gases form regenerating acid.
Further, adopt acid gas absorption tower to reclaim the first sour gas, acid gas absorption tower comprises bottom sour gas inlet mouth, top of tower water mouth spray and packing area, tower middle part, the first sour gas passes into from bottom sour gas inlet mouth, and contact in packing area with the absorption solution of acid gases spraying into from top of tower water mouth spray, form regenerating acid.
Further, the temperature of spray roasting is 500～600 ℃.
Further, absorption solution of acid gases is water.
Further, the mass percentage concentration of the spray flow control regenerating acid by absorption solution of acid gases is 18%～24%.
Further, before step S1, further comprise waste liquid is carried out to concentrated step.
Further, make Fe in waste liquid, Al mass of ion percentage total concn at 7%～9%, H by evaporation concentration
+mass percentage concentration lower than 10%.
Further, the elementary powdered iron ore of purifying treatment comprises: elementary powdered iron ore is carried out to heat treated, produce the second sour gas and secondary powdered iron ore; The second sour gas is reclaimed; And secondary powdered iron ore is added to mass percentage concentration is to react in 20%～35% sodium hydroxide solution, filter.
The temperature of further, elementary powdered iron ore being carried out to heat treated is 650～700 ℃.
Apply technical scheme of the present invention, first waste liquid is carried out to spray roasting, obtain the first sour gas and elementary powdered iron ore, and the first sour gas is reclaimed, the elementary powdered iron ore of purifying treatment, makes the acid in waste liquid be recycled by the recovery of sour gas, by iron, aluminum ion in the purifying treatment Recycling of waste liquid of elementary powdered iron ore, thereby can be for making Industrial products, the utilization of resources maximizes, and almost there is no secondary pollution deposits yields.
Accompanying drawing explanation
The Figure of description that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the process flow sheet of producing the treatment process of the waste liquid of aluminum oxide generation according to the acid system of the embodiment of the present invention.
Embodiment
It should be noted that, in the situation that not conflicting, the feature in embodiment and embodiment in the application can combine mutually.Describe below with reference to the accompanying drawings and in conjunction with the embodiments the present invention in detail.
For the deficiency of the acid method for treating waste liquid technology of tradition, the invention provides a kind of economy, environmental protection and can realize the technological method of utilization of wastewater resource, produce a treatment technology difficult problem for alumina technology waste water in order to solve acid system.
A kind of typical embodiment according to the present invention, provides a kind of acid system to produce the treatment process of the waste liquid of aluminum oxide generation.This treatment process comprises the following steps: S1, waste liquid is carried out to spray roasting, and obtain the first sour gas and elementary powdered iron ore; And S2, the first sour gas is reclaimed to the elementary powdered iron ore of purifying treatment.
Apply technical scheme of the present invention, first waste liquid is carried out to spray roasting, obtain the first sour gas and elementary powdered iron ore, and the first sour gas is reclaimed, the elementary powdered iron ore of purifying treatment, makes the acid in waste liquid be recycled by the recovery of sour gas, by iron, aluminum ion in the purifying treatment Recycling of waste liquid of elementary powdered iron ore, thereby can be for making Industrial products, the utilization of resources maximizes, and almost there is no secondary pollution deposits yields.
Preferably, to the first sour gas reclaim comprise the first sour gas is contacted with absorption solution of acid gases form regenerating acid, the so fully acid in Recycling of waste liquid.Concrete, can adopt acid gas absorption tower to reclaim the first sour gas, wherein, acid gas absorption tower comprises bottom sour gas inlet mouth, top of tower water mouth spray and packing area, tower middle part, the first sour gas passes into the absorption solution of acid gases spraying into from top of tower water mouth spray and contacts in packing area from bottom sour gas inlet mouth, forms regenerating acid.Sour gas enters from bottom, and absorption solution of acid gases sprays into and makes sour gas fully contact absorption with absorption solution of acid gases from top of tower water mouth spray.
Preferably, the temperature of spray roasting is 500～600 ℃.Under this warmly takes, aluminum chloride and iron(ic) chloride can Roasting Decompositions.A kind of typical embodiment according to the present invention, absorption solution of acid gases is water, this water is elected pure water as, can be evaporation meeting water in production process, and do not contain or contain a small amount of metal ion, can be the water that meets GB GB1146.1-89 to GB1146.11-89.Preferably, the mass percentage concentration of the spray flow control regenerating acid by absorption solution of acid gases (is 18%～24%, is mainly the quality percentage composition of hydrogenchloride.Regenerating acid in this concentration range can be directly used in the batching that chemical industry produces.According to the present invention, a kind of typical embodiment, before step S1, further comprises waste liquid is carried out to concentrated step, to save the needed fuel quantity of follow-up roasting.Preferably, make the quality percentage total concn of Fe in waste liquid, Al ion 7%～9% by evaporation concentration, the mass percentage concentration of free acid H+ is lower than 10%.
A kind of typical embodiment according to the present invention, the elementary powdered iron ore of purifying treatment comprises: elementary powdered iron ore is carried out to heat treated, produce the second sour gas and secondary powdered iron ore; The second sour gas is reclaimed; And secondary powdered iron ore is added to mass percent is the reaction of 20%～35% sodium hydroxide solution, filter.
Preferably, the temperature of elementary powdered iron ore being carried out to heat treated is 650～700 ℃, thoroughly carries out to guarantee to react.
Further illustrate beneficial effect of the present invention below in conjunction with embodiment.
In embodiment, process implementing process is as follows below:
One, the engineering construction of liquid waste disposal
(1) before processing structures powdered iron ore purifying treatment pond (adding caustic soda reaction tank), powdered iron ore purifying treatment and after processing, pile constructing of storage;
(2) support equipment is set
1) spray roasting part comprises: stoving oven (reactor), burner, cyclonic separator, crusher, stoving oven charging pump, the equipment such as gelled acid strainer.
2) acid gas absorption portion comprises: acid gas absorption tower, acid regeneration storage tank, Venturi preconcentrator and recycle pump, absorption tower charging pump etc.
3) powdered iron ore purifying treatment part comprises: powdered iron ore conveying fan, high-temperature spiral conveyor, caustic soda automatic sample equipment, windrow pond whipping appts, meticulous equipment for separating liquid from solid etc.
Two, process operation process
(1) spray roasting
1) stoving oven charging pump, with constant flow, by the spent acid through concentrated after filtering, is sprayed onto in stoving oven with certain pressure by furnace roof acid rifle and nozzle.
2) stoving oven, carbon steel material, inner lining refractory block.Heated by the burner being tangentially arranged on furnace bosh.The gas of burning forms spirrillum eddy current in reactor, drips and separates and evaporate spray into concentrated solution wherein from top.The chemical reaction of spent acid solution in stoving oven is as follows:
2FeCl
3+3H
2O→Fe
2O
3+6HCl
2AlCl
3+3H
2O→Al
2O
3+6HCl
3) the high-temperature roasting gas above-mentioned reaction being produced imports in cyclonic separator, again forms eddy flow.Under the effect of centrifugal force, separated and discharge by turning valve containing the brown iron oxide of a small amount of aluminum oxide.
(2) acid gas is recycled
1) in above-mentioned reaction, produce a large amount of hydrogen chloride gas, the in the situation that of high-temperature roasting, also there is water vapour to produce, the gas that these calcinations are produced passes into from acid absorption column bottom, fully contacts in filler region with the rinse water that spray into from top of tower, forms regenerating acid.
2) concentration of regenerating acid can be controlled by the flow that regulates spray water.
3) regenerating acid can be delivered to regenerating acid tank by pipeline, uses in order to follow-up batching stripping operation.
(3) purifying treatment of powdered iron ore
1) remove muriate: according to above-mentioned spray roasting technique, the main component in powdered iron ore is aluminum oxide, aluminum oxide and a small amount of muriate.For further reducing muriatic content in powdered iron ore, the powdered iron ore producing in stoving oven also needs further heat treated.This step is processed and is completed in burner high-temperature spiral conveyor (being dechlorination device), and Heating temperature is about 600 ℃ of left and right.By there being the blade spiral of two cover backwards rotation, combustion gases are fully mixed, remaining FeCl with powdered iron ore
3and AlCl
3meet high-temperature gas following chemical reaction occur:
2FeCl
3+3H
2O→Fe
2O
3+6HCl
2AlCl
3+3H
2O→Al
2O
3+6HCl
2) gas that above-mentioned treating processes produces enters sour absorption system, and the powdered iron ore producing is by pneumatic transport mode, is promoted to powdered iron ore processing to store up in pond, carries out subsequent disposal.
3) powdered iron ore purifying
Through the pyroprocessing of previous step, in powdered iron ore, be mainly brown iron oxide and aluminum oxide powder.For the aluminum oxide in purifying iron powder, removal powdered iron ore, add dense caustic soda (NaOH).Because aluminum oxide is intermediate oxide and ferric oxide is basic oxide, so only have aluminum oxide to react after adding alkali, be dissolved in solution, react as follows:
Al
2O
3+2NaOH→2NaAlO
2+H
2O
After having reacted, purer brown iron oxide can be obtained after filtration, steel mill's ironmaking can be delivered to; And the filtrate producing is contained the alternative calcium metaaluminate of a large amount of sodium metaaluminates in order to produce water purification agent.
Embodiment
The main flow process of the present embodiment as shown in Figure 1.
First, the waste water producing in acid oxidation aluminium technological process is concentrated, concentrated adopt industrial conventional evaporation technique, make Fe in waste liquid, Al total ion concentration 7%～9% by evaporation concentration, and free acid in waste liquid will be lower than 10%;
Secondly, the waste liquid after concentrated is directly delivered to and in stoving oven, carried out roasting by stoving oven charging pump.Maturing temperature, 550 ℃ of left and right, is taked fixed flow rate feeding (fixed according to concrete stoving oven treatment capacity).The reaction occurring in stoving oven is as follows:
2FeCl
3+3H
2O→Fe
2O
3+6HCl
2AlCl
3+3H
2O→Al
2O
3+6HCl
1), in roasting process, the first sour gas of generation reclaims after purifying treatment.Purified gas is mainly hydrogenchloride, is passed into acid gas absorption tower and reclaims, and concrete operations are as follows:
Hydrogen chloride gas after purifying is passed into from bottom, acid gas absorption tower, fully contact in filler region with the rinse water that spray into from top of tower (pure water, production process evaporation reuse water do not contain or contain a small amount of metal ion), form regenerating acid.The concentration of regenerating acid can be controlled by the flow that regulates spray water, general acidity is controlled, and in 18%～24% scope, (this concentration can be directly used in flyash " a step acid pasting " and produce aluminum oxide, the flyash in feed proportioning operation and mixed in hydrochloric acid batching.Regenerating acid is delivered to regenerating acid storage tank by pipeline, in order to using.So far, almost remove the roasting gas of HCl completely, maintain system negative pressure by waste gas conveying fan and discharge absorption tower.
2) in roasting process, the elementary powdered iron ore of generation is mainly ferric oxide and aluminum oxide, and a small amount of iron, aluminium muriate.For reducing muriatic content in powdered iron ore, the elementary powdered iron ore producing in stoving oven also needs further heating, and Heating temperature is 600 ℃ of left and right.This process completes in burner high-temperature spiral conveyor, by there being the lodicule spiral of two cover backwards rotation, combustion gases is fully mixed again, the FeCl in elementary powdered iron ore with elementary powdered iron ore
3and AlCl
3meet high-temperature gas following chemical reaction occur again:
2FeCl
3+3H
2O→Fe
2O
3+6HCl
2AlCl
3+3H
2O→Al
2O
3+6HCl
First the gas producing be discharged in independent cyclonic separator in order to separate the powdered iron ore of wherein carrying secretly, send back to subsequently the secondary powdered iron ore of acid absorption column generation by the mode of pneumatic transport, be promoted to secondary powdered iron ore and store up in pond, carry out next step purification process.
Caustic soda (NaOH) strong solution is joined to secondary powdered iron ore by a certain percentage by automatic sample equipment and store up in pond (add alkali number be powdered iron ore total amount 11%), and stir by transit mixer, about question response 30～40 minutes, be promoted to solid-liquid separation system with pump.
Solid-liquid separation adopts flame filter press, filter the solid obtaining and be purer brown iron oxide (iron level is in 70% left and right), and the main component of filtrate is sodium metaaluminate.
After liquid waste disposal, obtain the whereabouts of product: gas is mainly hydrogenchloride, return to Production Flow Chart by sour absorption system; Solid is brown iron oxide, because iron purity is higher in 70% left and right, so be good iron-smelting raw material, can directly deliver to steel mill and smelt iron; Liquid is mainly sodium metaaluminate liquid, is injecting the dirty liquid of a certain proportion of steaming (the aluminum chloride saturated solution that contains a small amount of impurity), water purification agent that just can manufacture level.
As a preferred embodiment, adopt technique scheme to produce alumina plant waste water to acid system and process, can process 1,000,000 tons/year of acid systems completely and produce the processing wastewater that alumina production line produces.Traditional wastewater treatment theory (environmental protection is sustained economic losses exactly) has been broken in this technological invention, and a difficult problem that had both solved Industrial Wastewater Treatment also can create beneficial result, reduce alumina production cost, and the profit of making profits in this project implementation year is 1,000 ten thousand yuan of left and right.By the processing of above technical scheme, acid system is produced alumina plant waste water and is all consumed or make product or the Cheng Huiyong that backflows, non-secondary pollution deposits yields: the hydrochloric acid in waste water turns back to batching stripping operation, iron in waste liquid, aluminum ion be respectively in order to production red iron oxide and sodium metaaluminate, and realized the maximum using of resource.
Technical scheme of the present invention is applied to processes the acid-bearing wastewater that acid system production alumina technology process produces, and can solve the difficult problem of the sector containing the industrial effluent processing of higher concentration iron, aluminum ion muriate and free acid.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. acid system is produced a treatment process for the waste liquid of aluminum oxide generation, it is characterized in that, comprises the following steps:
S1, carries out spray roasting by described waste liquid, obtains the first sour gas and elementary powdered iron ore; And
S2, reclaims described the first sour gas, elementary powdered iron ore described in purifying treatment.
2. treatment process according to claim 1, is characterized in that, to described the first sour gas reclaim comprise by described the first sour gas contact with absorption solution of acid gases form regenerating acid.
3. treatment process according to claim 2, it is characterized in that, adopt acid gas absorption tower to reclaim described the first sour gas, described acid gas absorption tower comprises bottom sour gas inlet mouth, top of tower water mouth spray and packing area, tower middle part, described the first sour gas passes into from described bottom sour gas inlet mouth, and contact in described packing area with the absorption solution of acid gases spraying into from described top of tower water mouth spray, form regenerating acid.
4. treatment process according to claim 1, is characterized in that, the temperature of described spray roasting is 500～600 ℃.
5. according to the treatment process described in claim 2 or 3, it is characterized in that, described absorption solution of acid gases is water.
6. treatment process according to claim 3, is characterized in that, is 18%～24% by the mass percentage concentration of regenerating acid described in the spray flow control of described absorption solution of acid gases.
7. treatment process according to claim 1, is characterized in that, before described step S1, further comprises described waste liquid is carried out to concentrated step.
8. treatment process according to claim 7, is characterized in that, by evaporation concentration make Fe in described waste liquid, Al mass of ion percentage total concn in the mass percentage concentration of 7%～9%, H+ lower than 10%.
9. treatment process according to claim 1, is characterized in that, elementary powdered iron ore comprises described in described purifying treatment:
Described elementary powdered iron ore is carried out to heat treated, produce the second sour gas and secondary powdered iron ore;
Described the second sour gas is reclaimed; And
It is to react in 20%～35% sodium hydroxide solution that described secondary powdered iron ore is added to mass percentage concentration, filters.
10. treatment process according to claim 9, is characterized in that, the temperature of described elementary powdered iron ore being carried out to heat treated is 650～700 ℃.
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| CN201310746760.2A CN103803495A (en) | 2013-12-30 | 2013-12-30 | Treatment method for liquid waste produced during the acid-process preparation of aluminum oxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271429A (en) * | 2015-10-27 | 2016-01-27 | 昆明理工大学 | Method for preparing iron oxide red and hydrochloric acid from hot galvanized waste acid |
| CN109432939A (en) * | 2018-11-06 | 2019-03-08 | 泰州华昊废金属综合利用有限公司 | The exhaust treatment system that Treatment of Metal Surface waste resource recovery utilizes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811711A (en) * | 2010-04-27 | 2010-08-25 | 中国神华能源股份有限公司 | Method for extracting aluminum oxide from fly ash |
| CN101844783A (en) * | 2010-04-27 | 2010-09-29 | 中国神华能源股份有限公司 | Method for dissolving aluminum out of circulating fluid bed coal ash |
| CN102674251A (en) * | 2012-04-28 | 2012-09-19 | 佛山津西金兰冷轧板有限公司 | Waste acid recovery and treatment process |
-
2013
- 2013-12-30 CN CN201310746760.2A patent/CN103803495A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811711A (en) * | 2010-04-27 | 2010-08-25 | 中国神华能源股份有限公司 | Method for extracting aluminum oxide from fly ash |
| CN101844783A (en) * | 2010-04-27 | 2010-09-29 | 中国神华能源股份有限公司 | Method for dissolving aluminum out of circulating fluid bed coal ash |
| CN102674251A (en) * | 2012-04-28 | 2012-09-19 | 佛山津西金兰冷轧板有限公司 | Waste acid recovery and treatment process |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271429A (en) * | 2015-10-27 | 2016-01-27 | 昆明理工大学 | Method for preparing iron oxide red and hydrochloric acid from hot galvanized waste acid |
| CN109432939A (en) * | 2018-11-06 | 2019-03-08 | 泰州华昊废金属综合利用有限公司 | The exhaust treatment system that Treatment of Metal Surface waste resource recovery utilizes |
| CN109432939B (en) * | 2018-11-06 | 2024-01-16 | 泰州华昊废金属综合利用有限公司 | Waste gas treatment system for recycling metal surface treatment waste |
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Application publication date: 20140521 |