CN103435078A - Method for dissolving out aluminum by coal ash acid process and equipment system for method - Google Patents
Method for dissolving out aluminum by coal ash acid process and equipment system for method Download PDFInfo
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- CN103435078A CN103435078A CN2013103847335A CN201310384733A CN103435078A CN 103435078 A CN103435078 A CN 103435078A CN 2013103847335 A CN2013103847335 A CN 2013103847335A CN 201310384733 A CN201310384733 A CN 201310384733A CN 103435078 A CN103435078 A CN 103435078A
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Abstract
The invention discloses a method for dissolving out aluminum by a coal ash acid process. The method comprises the following steps: (1) adding water to coal ash to obtain coal ash slurry; (2) respectively heating the coal ash slurry and an acid solution to 40-70 DEG C, and preheating; (3) respectively adding the preheated coal ash slurry and the acid solution to a reaction kettle to obtain mixed slurry; and (4) keeping the mixed slurry at temperature of 125 to 160 DEG C for 1.5 to 3 hours, and then performing the aluminum dissolve-out reaction. By adopting the method, the service life of equipment can be greatly prolonged, and the cost of equipment can be decreased. The invention also discloses an equipment system for dissolving out the aluminum by the coal ash acid process.
Description
Technical field
The present invention relates to the recycling of flyash, the method that is specifically related to acid system Aluminum from flyash reaches the device systems for the method.
Background technology
Flyash is that coal-burning power plant produces, the industrial solid castoff material of quantity discharged maximum.In flyash, the content of aluminum oxide is often very high, and the flyash in a lot of areas is salic aluminous fly-ash more than 30%, wherein in the flyash of certain areas alumina content up to 50%.Aluminum oxide is the important source material of producing metallic aluminium, is also a kind of important Chemicals, extracts aluminum oxide from flyash, is solution bauxite resource deficiency, realizes one of effective way of total utilization of PCA.
The current domestic single current method Aluminum from flyash of mainly taking, at first the method mixes flyash and acid solution in dosing vessel, forms mixed slurry, described mixed slurry is delivered to reactor by transferpump and transport pipe and carries out the high temperature stripping.Discharge reaction heat while mixing with acid solution due to dry flyash, thereby the temperature of mixed slurry sharply raises when batching, even can reach the boiling point of water, such high temperature has reduced the work-ing life of equipment; Simultaneously due to the abrasiveness of flyash and the acid etching of acid solution, the mixed slurry that makes flyash and acid solution be mixed to form not only has abrasiveness but also have acid etching, thereby dosing vessel (particularly its stirring rake), transferpump and transport pipe are all caused serious harm, service life of equipment is short, for example only have 2 months the work-ing life of the stirring rake of dosing vessel, the work-ing life of transferpump, general less than was 2 months.
Therefore, need a kind of work-ing life that can improve equipment, reduce the method for the flyash acid system Aluminum of equipment cost.
Summary of the invention
A first aspect of the present invention purpose is to provide a kind of method of flyash acid system Aluminum, to improve the work-ing life of equipment, reduces equipment cost.
A second aspect of the present invention purpose is to improve a kind of device systems for described method.
A first aspect of the present invention purpose is achieved by the following technical solution:
A kind of method of flyash acid system Aluminum comprises:
(1) flyash is added to water and be mixed with the flyash slip;
(2) flyash slip and acid solution are warming up to respectively to 40 ℃～70 ℃ and carry out preheating;
(3) the flyash slip after preheating and acid solution are added respectively in reactor and form mixed slurry; With
(4) described mixed slurry is incubated under 125 ℃～160 ℃ to the stripping reaction that 1.5h～3h carries out aluminium.
Preferably, the solid content of described flyash slip is 40%～60%.
Preferably, described acid solution is hydrochloric acid or sulphuric acid soln, and the mass concentration of wherein said hydrochloric acid is 28%～37%, and the mass concentration of described sulfuric acid is 40～60%.
Preferably, react and directly or indirectly heat by water vapor described in step (4).
Preferably, described flyash is circulating fluid bed coal ash or through the coal-powder boiler flyash of overactivation.
Preferably, described mixed slurry is at least reacting in the two-stage reaction still, and step (4) comprises to the step that passes into the water vapor of 140 ℃～170 ℃ in first step reactor at least.
With existing single current method technique of Aluminum from flyash, compare, the advantage of the inventive method is:
1. at first flyash added to water and be configured to the flyash slip, and flyash slip and acid solution are carried out respectively to preheating, such setting has avoided dry flyash directly to mix the infringement of the high temperature of generation to equipment and materials with acid solution, has extended the work-ing life of equipment; Pre-heating step can make mixed slurry reach fast preset temp in reactor.
Flyash slip and acid solution respectively the delivery system by separately add and mixed in reactor and react, such processing makes the flyash slip separate before reaction with acid solution, only produce a kind of in abrasion and acid etching infringement for dosing vessel, transferpump and transport pipe separately, thereby the infringement that equipment is caused will be far smaller than flyash slip and acid solution in prior art and be pre-mixed abrasion and the dual infringement of acid etching that dosing vessel stirring rake, transferpump and transport pipe are produced, greatly extended the work-ing life of described equipment.
Purpose according to a second aspect of the invention, a kind of device systems for flyash acid system Aluminum also is provided, comprise the flyash dosing vessel, transferpump and the first cannula primary heater that connect successively with transport pipe, the sour storage tank connected successively with transport pipe, acid proof pump and the second cannula primary heater, and reactor, the discharge end of the discharge end of described the first cannula primary heater and described the second cannula primary heater all is connected with the opening for feed of reactor.
Preferably, described reactor is at least two-stage reaction still, more preferably two-stage, three grades or fourth-order reaction still.
Preferably, described transferpump is stainless steel, and described the first cannula primary heater adopts carbon steel, and described acid proof pump is that fluorine is moulded the alloy material.
The existing single current method device systems that Aluminum is used from flyash, generally include the dosing vessel that mixes with acid solution for flyash, for mixed slurry being delivered to transferpump and the reactor of reactor, wherein dosing vessel, transferpump and transport pipe are when adopting common material, and work-ing life is shorter; When using wear-resisting, acidproof material, can greatly increase equipment cost again.By comparison, the present device system is by being processed acid solution and flyash slip and carried with e-quipment and pipe independently, make each equipment without adopting expensive wear-resisting, acidproof material, and greatly extend work-ing life on the contrary, equipment cost reduces more than 30%.
The accompanying drawing explanation
Fig. 1 shows the schematic flow sheet according to the method for the flyash acid system Aluminum of one embodiment of the present invention.
Fig. 2 shows the schematic diagram according to the device systems for flyash acid system Aluminum of one embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention will be further described, but therefore the present invention is not subject to any restriction.In the situation that do not depart from the scope of design of the present invention and restriction, the present invention can have other distortion.
Fig. 1 shows the method according to the flyash acid system Aluminum of one embodiment of the present invention.
Referring to Fig. 1, flyash is added to water in the flyash dosing vessel and is mixed with the flyash slip, by transferpump by the flyash slurry pipeline transport to the flyash cannula primary heater, be preheated to 40 ℃～70 ℃; Preparating acid solution in the acid solution storage tank, be delivered to the acid solution cannula primary heater by acid proof pump by described acid solution, is preheated to 40 ℃～70 ℃; The flyash slip and the acid solution that complete preheating are inputted in reactor by transport pipe separately respectively, be mixed into mixed slurry, then be incubated 1.5h～3h under 125 ℃～160 ℃, carry out the stripping reaction of aluminium, the mixed slurry after stripping adds water and is diluted and be cooled to below 120 ℃.
Compared with prior art, the inventive method can avoid preparing burden reaction heat to the infringement of equipment and materials, the work-ing life of extension device; Flyash slip and the acid solution delivery system by separately respectively add and are mixed in reactor and react, thereby only produce a kind of in abrasion and acid etching infringement for dosing vessel, transferpump and transport pipe separately, the infringement that equipment is caused will be far smaller than flyash slip and acid solution in prior art and be pre-mixed abrasion and the dual infringement of acid etching that dosing vessel stirring rake, transferpump and transport pipe are produced, and greatly extended the work-ing life of described equipment; Use the inventive method also to avoid using simultaneously acidproof, wear-resisting expensive material, make equipment cost reduce more than 30%.
Preferably, the solid content of described flyash slip is 40%～60%.When being greater than 60%, solid content can cause difficulty to the conveying of pump; Solid content lower than 40% the time, needs the acid solution of high density; Take described solid content, can guarantee the smooth delivery of power of flyash slip, and the solubility rate of aluminum oxide can reach 60～70%, this is useful especially for extracting aluminum oxide in industrial residue flyash.
Preferably, the acid solution that the inventive method is used is hydrochloric acid or sulphuric acid soln, and preferably the mass concentration of hydrochloric acid is 28%～37%, and the mass concentration of sulfuric acid is 40～60%.
In the inventive method, can make mixed slurry be warming up to preset temperature by any type of heating.Preferably, by water vapor being passed into to direct heating in the mixed slurry in reactor, or water vapour is passed into to indirect heating in the outer heating jacket of reactor realize.
Preferably, the inventive method comprises at least two-stage reaction still, and with the water vapor of 140 ℃～170 ℃, first step reactor is at least carried out to direct heating or indirect heating.For example the inventive method can comprise the third order reaction still, mixed slurry passes through first step reactor, second stage reactor and third stage reactor successively, the water vapors of 140 ℃～170 ℃ are passed in first step reactor and carry out direct heating, the second stage and third stage reactor can determine whether according to actual temperature conditions heating, as long as the temperature of three reactors all remains on 125 ℃～160 ℃, react.
Preferably, described flyash is circulating fluid bed coal ash or through the coal-powder boiler flyash of overactivation.The flyash chief component composition that circulating fluidized bed technique obtains comprises aluminum oxide, and has good activity, and easy and acid-respons is applicable to adopting the acid system stripping; The flyash of other types, coal-powder boiler flyash for example, activity is lower usually, need to after overactivation, carry out sour stripping reaction again.
Fig. 2 shows the schematic diagram according to the device systems for flyash acid system Aluminum of one embodiment of the present invention.
Referring to Fig. 2, device systems for flyash acid system Aluminum of the present invention comprises flyash dosing vessel, transferpump and the first cannula primary heater connected successively with transport pipe, the sour storage tank connected successively with transport pipe, acid proof pump and the second cannula primary heater, and reactor, the discharge end of the discharge end of described the first cannula primary heater and described the second cannula primary heater all is connected with the opening for feed of reactor.
Described reactor can adopt multi-stage reacting kettle, for example secondary, three grades, fourth-order reaction still.
Described transferpump can adopt general stainless steel, and the material of described the first cannula primary heater can adopt general steel pipe, such as carbon steel tubing; Described acid proof pump selects fluorine to mould the alloy material, and described the second cannula primary heater can be selected the preheater of general acidproof material.
Below by specific embodiment, implementation method of the present invention is further described, but embodiment is not construed as limiting the present invention.Following examples are all usingd circulating fluid bed coal ash as the raw material of flyash acid pasting Aluminum of the present invention, and the main chemical compositions of this flyash is as shown in table 1.
Table 1 circulating fluid-bed chemical composition of PCA (wt%)
| SiO 2 | Al 2O 3 | TiO 2 | CaO | MgO | Fe 2O 3 | K 2O | Na 2O | LOI | Summation |
| 35.70 | 51.34 | 2.19 | 3.43 | 0.44 | 2.04 | 0.24 | 0.28 | 3.29 | 98.95 |
Embodiment 1
Circulating fluid bed coal ash is added to water and be mixed with the flyash slip that solid content is 40%, stir in dosing vessel.The flyash slip is transported to cannula primary heater with the transferpump of stainless steel, and is warming up to 70 ℃; In sour storage tank, the preparation mass concentration is 37% hydrochloric acid, and the acid proof pump of moulding the alloy material with fluorine is transported in acidproof preheater and is warming up to 40 ℃.The hydrochloric acid of the flyash slip after preheating and 37% is joined respectively in the stripping reactor, and in hydrochloric acid, the mass ratio of hydrogenchloride and flyash is 0.6:1; Adopt the two-stage reaction still, mixed slurry passes through first step reactor and second stage reactor successively, and the water vapor of 140 ℃ is passed into respectively to direct heating in first step reactor and second stage reactor, makes mixed slurry be warming up to 125 ℃, and insulation 3h, make the aluminium stripping in flyash; Mixed slurry after stripping adds water and is diluted and be cooled to below 120 ℃.After measured, in flyash, digesting efficiency of alumina is 50%.Long period is moved 90 days continuously, and dosing vessel stirring rake, slurry delivery pump and acid proof pump all can normally use.
Embodiment 2
Circulating fluid bed coal ash is added to water and be mixed with the flyash slip that solid content is 50%, stir in dosing vessel.The flyash slip is transported to cannula primary heater with the stainless steel transferpump, and is warming up to 50 ℃; In sour storage tank, the preparation mass concentration is 32% hydrochloric acid, and the acid proof pump of moulding the alloy material with fluorine is transported in acidproof preheater and is warming up to 70 ℃.The hydrochloric acid of the flyash slip after preheating and 32% is joined respectively in the stripping reactor, and in hydrochloric acid, the mass ratio of hydrogenchloride and flyash is 0.6:1; Adopt the two-stage reaction still, mixed slurry passes through first step reactor and second stage reactor successively, and the water vapor of 150 ℃ is passed into respectively to direct heating in first step reactor and second stage reactor, makes mixed slurry be warming up to 130 ℃, and insulation 2h, make the aluminium stripping in flyash; Mixed slurry after stripping adds water and is diluted and be cooled to below 120 ℃.After measured, in flyash, digesting efficiency of alumina is 52%.Long period is moved 90 days continuously, and dosing vessel stirring rake, slurry delivery pump and acid proof pump all can normally use.
Embodiment 3
Circulating fluid bed coal ash is added to water and be mixed with the flyash slip that solid content is 60%, stir in dosing vessel.The flyash slip arrives cannula primary heater by the stainless steel pump delivery, and is warming up to 40 ℃; In sour storage tank, the preparation mass concentration is 28% hydrochloric acid, and the acid proof pump of moulding the alloy material with fluorine is transported in acidproof preheater and is warming up to 70 ℃.Adopt double stream process that the hydrochloric acid of the flyash slip after preheating and 28% is joined respectively in the stripping reactor, in hydrochloric acid, the mass ratio of hydrogenchloride and flyash is 0.6:1; Adopt the two-stage reaction still, mixed slurry passes through first step reactor and second stage reactor successively, and the water vapor of 170 ℃ is passed into to direct heating in first step reactor, makes mixed slurry be warming up to 140 ℃, and insulation 3h, makes the aluminium stripping in flyash; Mixed slurry after stripping adds water and is diluted and be cooled to below 120 ℃.After measured, in flyash, digesting efficiency of alumina is 55%.Long period is moved 90 days continuously, and dosing vessel stirring rake, slurry delivery pump and acid proof pump all can normally use.
Embodiment 4
Circulating fluid bed coal ash is added to water and be mixed with the flyash slip that solid content is 50%, stir in dosing vessel.The flyash slip arrives cannula primary heater by the stainless steel pump delivery, and is warming up to 50 ℃; The preparation mass concentration sulfuric acid that is 40% in sour storage tank, the acid proof pump of moulding the alloy material with fluorine is transported in acidproof preheater and is warming up to 70 ℃.The sulfuric acid of the flyash slip after preheating and 37% is joined respectively in the stripping reactor to H in sulfuric acid
2sO
4with the mass ratio of flyash be 1.6:1; Adopt the two-stage reaction still, mixed slurry passes through first step reactor and second stage reactor successively, and the water vapor of 150 ℃ is passed into to direct heating in first step reactor, makes mixed slurry be warming up to 130 ℃, and insulation 1.5h, makes the aluminium stripping in flyash; Mixed slurry after stripping adds water and is diluted and be cooled to below 120 ℃.After measured, in flyash, digesting efficiency of alumina is 57%.Long period is moved 90 days continuously, and dosing vessel stirring rake, slurry delivery pump and acid proof pump all can normally use.
Embodiment 5
Circulating fluid bed coal ash is added to water and be mixed with the flyash slip that solid content is 40%, stir in dosing vessel.The flyash slip arrives cannula primary heater by the stainless steel pump delivery, and is warming up to 60 ℃; The preparation mass concentration sulfuric acid that is 50% in sour storage tank, the acid proof pump of moulding the alloy material with fluorine is transported in acidproof preheater and is warming up to 60 ℃.The sulfuric acid of the flyash slip after preheating and 37% is joined respectively in the stripping reactor to H in sulfuric acid
2sO
4with the mass ratio of flyash be 1.6:1; Adopt the two-stage reaction still, mixed slurry passes through first step reactor and second stage reactor successively, and the water vapor of 170 ℃ is passed into to direct heating in first step reactor, makes mixed slurry be warming up to 160 ℃, and insulation 1.5h, makes the aluminium stripping in flyash; Mixed slurry after stripping adds water and is diluted and be cooled to below 120 ℃.After measured, in flyash, digesting efficiency of alumina is 57%.Long period is moved 90 days continuously, and dosing vessel stirring rake, slurry delivery pump and acid proof pump all can normally use.
Claims (10)
1. the method for a flyash acid system Aluminum comprises:
(1) flyash is added to water and be mixed with the flyash slip;
(2) flyash slip and acid solution are warming up to respectively to 40 ℃～70 ℃ and carry out preheating;
(3) the flyash slip after preheating and acid solution are added respectively in reactor and form mixed slurry; With
(4) described mixed slurry is incubated under 125 ℃～160 ℃ to the stripping reaction that 1.5h～3h carries out aluminium.
2. method according to claim 1, is characterized in that, the solid content of described flyash slip is 40%～60%.
3. method according to claim 1, is characterized in that, described acid solution is hydrochloric acid or sulphuric acid soln, and the mass concentration of wherein said hydrochloric acid is 28%～37%, and the mass concentration of described sulfuric acid is 40～60%.
4. method according to claim 1, is characterized in that, described in step (4), reacts and directly or indirectly heat by water vapor.
5. method according to claim 1, is characterized in that, described flyash is circulating fluid bed coal ash or through the coal-powder boiler flyash of overactivation.
6. according to the described method of any one in claim 1-5, it is characterized in that, described mixed slurry is at least reacting in the two-stage reaction still, and step (4) comprises to the step that passes into the water vapor of 140 ℃～170 ℃ in first step reactor at least.
7. the device systems for the described method of claim 1-6 any one, comprise the flyash dosing vessel, transferpump and the first cannula primary heater that connect successively with transport pipe, the sour storage tank connected successively with transport pipe, acid proof pump and the second cannula primary heater, and reactor, the discharge end of the discharge end of described the first cannula primary heater and described the second cannula primary heater all is connected with the opening for feed of reactor.
8. device systems according to claim 7, is characterized in that, described reactor is two-stage reaction still at least.
9. device systems according to claim 8, is characterized in that, described reactor is two-stage, three grades or fourth-order reaction still.
10. according to the described device systems of claim 7-9 any one, it is characterized in that, described transferpump is stainless steel, and described the first cannula primary heater is carbon steel, and described acid proof pump is that fluorine is moulded the alloy material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925594A (en) * | 2015-12-29 | 2017-07-07 | 中国神华能源股份有限公司 | A kind of processing method of flyash acid dissolution slag |
| CN109354045A (en) * | 2018-11-08 | 2019-02-19 | 中国神华能源股份有限公司 | A method of lithium carbonate is prepared using dirty mother liquor is steamed |
| CN110745850A (en) * | 2019-11-29 | 2020-02-04 | 神华准能资源综合开发有限公司 | Ferrous oxidation method and system for extracting aluminum oxide from fly ash by acid process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090032806A (en) * | 2007-09-28 | 2009-04-01 | 한국전력공사 | Extraction method and apparatus of high pure alumina from fly ash using microwave |
| CN101863497A (en) * | 2010-04-27 | 2010-10-20 | 中国神华能源股份有限公司 | Mixing heating acid dissolving method and device for fly ash slurry |
| CN102241410A (en) * | 2010-05-14 | 2011-11-16 | 东北大学 | Ecological synthetic utilization method of fly ash |
| CN102659155A (en) * | 2012-04-25 | 2012-09-12 | 吉林大学 | Low-temperature acid soluble method for leaching alumina from fly ash |
-
2013
- 2013-08-29 CN CN201320533277.1U patent/CN203411348U/en not_active Expired - Lifetime
- 2013-08-29 CN CN2013103847335A patent/CN103435078A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090032806A (en) * | 2007-09-28 | 2009-04-01 | 한국전력공사 | Extraction method and apparatus of high pure alumina from fly ash using microwave |
| CN101863497A (en) * | 2010-04-27 | 2010-10-20 | 中国神华能源股份有限公司 | Mixing heating acid dissolving method and device for fly ash slurry |
| CN102241410A (en) * | 2010-05-14 | 2011-11-16 | 东北大学 | Ecological synthetic utilization method of fly ash |
| CN102659155A (en) * | 2012-04-25 | 2012-09-12 | 吉林大学 | Low-temperature acid soluble method for leaching alumina from fly ash |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925594A (en) * | 2015-12-29 | 2017-07-07 | 中国神华能源股份有限公司 | A kind of processing method of flyash acid dissolution slag |
| CN109354045A (en) * | 2018-11-08 | 2019-02-19 | 中国神华能源股份有限公司 | A method of lithium carbonate is prepared using dirty mother liquor is steamed |
| CN110745850A (en) * | 2019-11-29 | 2020-02-04 | 神华准能资源综合开发有限公司 | Ferrous oxidation method and system for extracting aluminum oxide from fly ash by acid process |
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Application publication date: 20131211 |