CN109336154A - A method of using coal ash for manufacturing for crystalline sulfuric acid aluminium - Google Patents
A method of using coal ash for manufacturing for crystalline sulfuric acid aluminium Download PDFInfo
- Publication number
- CN109336154A CN109336154A CN201811365048.7A CN201811365048A CN109336154A CN 109336154 A CN109336154 A CN 109336154A CN 201811365048 A CN201811365048 A CN 201811365048A CN 109336154 A CN109336154 A CN 109336154A
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- flyash
- coal ash
- manufacturing
- aluminum sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
- C01F7/743—Preparation from silicoaluminious materials, e.g. clays or bauxite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method of using coal ash for manufacturing for crystalline sulfuric acid aluminium, belong to Technology of Comprehensive Utilization of Coal Ash field, it can solve the problems such as current coal ash for manufacturing heats pressurized acid leaching process and evaporating concentration process there are energy consumptions high, at high cost, complex process for aluminum sulfate technique, include the following steps: that (1) flyash carries out iron removal by magnetic separation after mechanical lapping, obtains iron power removing coal ash；(2) flyash self-heating presses acidleach certainly；(3) it is separated by solid-liquid separation；(4) leachate is adjusted and self-heating is concentrated by evaporation；(5) crystalline sulfuric acid aluminium crystal can be obtained in crystallisation by cooling and crushing.Especially flyash vitriol lixiviation and aluminum sulfate leachate evaporating concentration process carry out the present invention by sulfuric acid dilution heat release and exothermic heat of reaction in entire technical process, do not need external heat, low energy consumption, at low cost, and technical process is simple, easy to promote and utilize.
Description
Technical field
The invention belongs to Technology of Comprehensive Utilization of Coal Ash fields, and in particular to for one kind using flyash as raw material, short route is low
The method that cost prepares crystalline sulfuric acid aluminium.
Background technique
Currently, flyash is mainly used for the fields such as building materials, building, added value is low, and economic benefit is unobvious.From flyash
From the point of view of composition, aluminium oxide+silica content accounts for 80% or more, the oxygen especially in the flyash in the areas such as China Jin Bei, illiteracy west
Change aluminium content and reaches 50% or more, great extraction value.In recent years, from aluminous fly-ash extract aluminium oxide, crystal aluminum chloride,
The products such as crystalline sulfuric acid aluminium become one of the important directions of flyash higher value application, are not only able to alleviate China's bauxite resource
The trend of shortage, moreover it is possible to mitigate pollution of the flyash to environment, it is most important that flyash is turned waste into wealth, comprehensive utilization is realized,
It has broad application prospects.
Aluminum sulfate application range is extremely extensive, is mainly used for the purification of drinking water, trade effluent waste water, or without alkali cement
The primary raw material of accelerator.It is mainly at present that flyash is added by sulfuric acid using flyash as the method that raw material prepares crystalline sulfuric acid aluminium
Hot pressurized acid leaching-evaporation and concentration-crystallisation by cooling finally obtains crystalline sulfuric acid aluminium.CN200810011311.2 discloses one kind with powder
Coal ash is the method that raw material prepares aluminum sulfate, and this method leaches flyash using the method for sulfuric acid heating pressure leaching, generates alkali
Formula aluminum sulfate, regulation system basicity and pH value after being then separated by solid-liquid separation are concentrated by evaporation, obtain aluminum sulfate after crystallisation by cooling.
On this basis, CN201010601142, CN201010601181, CN201010601611, which combine, discloses one kind with flyash
The method for preparing low iron high-purity sulphuric acid aluminium and its comprehensive utilization, flyash is removed through mechanical activation, flotation except carbon, magnetic separation in this method
After iron, aluminum sulfate leachate is obtained through sulfuric acid heating pressure leaching, leachate is concentrated, acid is washed in Organic Alcohol alcoholization, except iron, dehydration
Low iron high-purity sulphuric acid aluminium is obtained after drying.As can be seen that flyash heating pressurization leaching from the technique that above-mentioned several patents are mentioned
Process temperature respectively reaches 120 ~ 230 DEG C and 200 ~ 240 DEG C out, not only needs through external heat, and energy consumption is high, and for setting
Standby requirement is also high；It requires to adjust concentration by evaporation and concentration in addition, obtaining aluminum sulfate leachate in above-mentioned patent, equally
There is a problem of that energy consumption is high, at high cost.Therefore, one kind is developed using flyash as raw material and reaction system mildly prepares crystalline sulfuric acid
The comprehensive utilization high-valued for flyash of the method for aluminium has great importance.
Summary of the invention
The present invention heats pressurized acid leaching process for current coal ash for manufacturing for aluminum sulfate technique and evaporating concentration process exists
The problems such as energy consumption is high, at high cost, complex process, proposes to pass through sulfuric acid using circulating fluid bed coal ash as raw material and dilute heat release leaching
The aluminium in flyash obtains aluminum sulfate solution out, and aluminum sulfate solution adjusts acidity while passing through reaction and puts by addition aluminium hydroxide
The further concentrate solution of heat, is most prepared crystalline sulfuric acid aluminium through crystallisation by cooling afterwards, whole process of the present invention does not need external source and adds
Heat, low energy consumption, at low cost, and technical process is simple, easy to promote and utilize.
The present invention adopts the following technical scheme:
A method of using coal ash for manufacturing for crystalline sulfuric acid aluminium, include the following steps:
Iron removal by magnetic separation: the first step after flyash mechanical lapping, carries out iron removal by magnetic separation, obtains the flyash except iron；
Second step, sulfuric acid self-heating press acidleach certainly: flyash and water uniformly being mixed in proportion, by the concentrated sulfuric acid in proportion to mixture
In be added portionwise, carry out acid-leaching reaction, obtain mixed solution；
Third step is separated by solid-liquid separation: after acid-leaching reaction is complete, the water that temperature is greater than 80 DEG C is proportionally added into mixed solution, is taken advantage of
Heat is separated by solid-liquid separation, and is obtained aluminum sulfate leachate and be can be used as the leached mud of cement admixture；
4th step, leachate is adjusted and self-heating is concentrated by evaporation: added into aluminum sulfate leachate aluminium hydroxide be adjusted to 1 to pH ~
4, while obtaining the aluminum sulfate concentrate by being evaporated concentration using exothermic heat of reaction；
5th step, crystallisation by cooling: by aluminum sulfate concentrate crystallisation by cooling, obtaining crystalline sulfuric acid aluminium, and aluminum sulfate production is obtained after crushing
Product.
Partial size after flyash mechanical lapping described in the first step is 100 ~ 400 mesh.
Sulfuric acid self-heating described in second step carries out in enamel glass reaction kettle from pressure acidleach, the mass ratio of flyash and water
For 1:0.5 ~ 1:3, the mass ratio of the concentrated sulfuric acid and flyash is 0.5:1 ~ 5:1, and the temperature of acid-leaching reaction is 120 ~ 180 DEG C, pressure
For 0.1 ~ 0.6MPa, the reaction time is 1 ~ 8h.
Further, sulfuric acid self-heating described in second step from pressure acidleach carried out in enamel glass reaction kettle, flyash and
The mass ratio of water is 1:0.6 ~ 1:1.5, and the mass ratio of the concentrated sulfuric acid and flyash is 1:1 ~ 3:1, the temperature of acid-leaching reaction is 130 ~
160 DEG C, pressure is 0.2 ~ 0.4MPa.
The method of separation of solid and liquid described in third step include self-heating sedimentation separation, plate compression separation, vacuum filtration and from
The heart separation in any one.
The mass ratio of quality and flyash that water is added in third step is 1.25:1 ~ 2:1.
Further, aluminium hydroxide is added described in the 4th step into aluminum sulfate leachate and is adjusted to 2 ~ 3 to pH.
40 DEG C of the temperature < of crystallisation by cooling described in 5th step.
Beneficial effects of the present invention are as follows:
1. especially flyash vitriol lixiviation and aluminum sulfate leachate evaporating concentration process leans in entire technical process of the invention
Sulfuric acid dilutes heat release and exothermic heat of reaction carries out, and does not need external heat, low energy consumption, at low cost, and technical process is simple, convenient for pushing away
Wide application.
2. the purity of the crystalline sulfuric acid aluminium prepared using preparation method of the invention is up to 95.2%.
Detailed description of the invention
Fig. 1 is the XRD spectrum of solution aluminum sulfate prepared by the embodiment of the present invention 1.
Specific embodiment
All circulating fluid bed coal ash constituent analyses are as follows in following embodiments:
Embodiment 1
(1) iron removal by magnetic separation: after flyash mechanical lapping to 200 mesh, iron removal by magnetic separation is carried out, obtains the flyash except iron.
(2) sulfuric acid self-heating is from pressing acidleach: in enamel glass reactor by flyash according to weight ratio be 1:0.7 and water into
Then row mix is that 1:1 is added portionwise into mixture with flyash weight ratio according to the concentrated sulfuric acid, reaches to pressure
0.3MPa, temperature react 3h when reaching 140 DEG C.
(3) it is separated by solid-liquid separation: after complete reaction, being added for 1.25:1 to Leaching Systems by the mass ratio of water and flyash
Water is uniformly mixed to solution system, is separated by solid-liquid separation using plate and frame filter press, obtains aluminum sulfate leachate (quality of alumina
Score is 7.5%) and leached mud, leached mud can be directly as cement admixtures.
(4) leachate is adjusted and self-heating is concentrated by evaporation: the aluminum sulfate leachate that above-mentioned steps are obtained passes through addition hydrogen-oxygen
Change aluminium and carry out constituent adjustment, pH value is adjusted to 2.0, while being evaporated concentration using exothermic heat of reaction, obtain salic be
15.8% aluminum sulfate concentrate.
(5) crystallisation by cooling: will crystallize at 20 DEG C of the cooling of aluminum sulfate concentrate, obtain crystalline sulfuric acid aluminium, remaining without solution.
Conjugate stream calculation is analyzed after tested, and the comprehensive recovery of aluminium reaches 84.5%, and the purity of crystalline sulfuric acid aluminium reaches
95.2%, XRD spectrum is as shown in Figure 1.From can be with 13.47 °, 19.87 °, 21.57 °, 26.27 ° and 29. 64 ° of sample in figure
There is apparent diffraction maximum, consistent with the characteristic diffraction peak of aluminum sulfate octadecahydrate, diffraction maximum is stronger, illustrates the knot of aluminum sulfate octadecahydrate
Brilliant degree is good.
Embodiment 2
(1) iron removal by magnetic separation: after flyash mechanical lapping to 100 mesh, iron removal by magnetic separation is carried out, obtains the flyash except iron.
(2) sulfuric acid self-heating presses acidleach certainly: carrying out flyash for 1:1 and water according to weight ratio in enamel glass reactor
Then mix is that 1.5:1 is added portionwise into mixture with flyash weight ratio according to the concentrated sulfuric acid, reaches to pressure
0.35MPa, temperature react 4h when reaching 160 DEG C.
(3) it is separated by solid-liquid separation: after complete reaction, water is added to Leaching Systems for 1.5:1 by the mass ratio of water and flyash,
It is uniformly mixed to solution system, is separated by solid-liquid separation using plate and frame filter press, obtains aluminum sulfate leachate (quality of alumina score
7.8%) and leached mud, leached mud can be directly as cement additives for.
(4) leachate is adjusted and self-heating is concentrated by evaporation: the aluminum sulfate leachate that above-mentioned steps are obtained passes through addition hydrogen-oxygen
Change aluminium and carry out constituent adjustment, pH value is adjusted to 2.5, while being evaporated concentration using exothermic heat of reaction, obtain salic be
16.0% aluminum sulfate concentrate.
(5) crystallisation by cooling: will crystallize at 25 DEG C of the cooling of aluminum sulfate concentrate, obtain crystalline sulfuric acid aluminium, remaining without solution.
Conjugate stream calculation is analyzed after tested, and the comprehensive recovery of aluminium reaches 87.5%, and the purity of crystalline sulfuric acid aluminium reaches
94.1%。
Embodiment 3
(1) iron removal by magnetic separation: after flyash mechanical lapping to 300 mesh, iron removal by magnetic separation is carried out, obtains the flyash except iron.
(2) sulfuric acid self-heating is from pressing acidleach: in enamel glass reactor by flyash according to weight ratio be 1:0.8 and water into
Then row mix is that 2:1 is added portionwise into mixture with flyash weight ratio according to the concentrated sulfuric acid, reaches to pressure
0.4MPa, temperature react 6h when reaching 160 DEG C.
(3) it is separated by solid-liquid separation: after complete reaction, water is added to Leaching Systems for 2:1 by the mass ratio of water and flyash, to
Solution system is uniformly mixed, and is separated by solid-liquid separation using plate and frame filter press, and obtaining aluminum sulfate leachate, (quality of alumina score is
7.8%) and leached mud, leached mud can be directly as cement additives.
(4) leachate is adjusted and self-heating is concentrated by evaporation: the aluminum sulfate leachate that above-mentioned steps are obtained passes through addition hydrogen-oxygen
Change aluminium and carry out constituent adjustment, pH value is adjusted to 2.6, while being evaporated concentration using exothermic heat of reaction, obtain salic be
16.0% aluminum sulfate concentrate.
(5) crystallisation by cooling: will crystallize at 30 DEG C of the cooling of aluminum sulfate concentrate, obtain crystalline sulfuric acid aluminium, remaining without solution.
Conjugate stream calculation is analyzed after tested, and the comprehensive recovery of aluminium reaches 89.5%, and the purity of crystalline sulfuric acid aluminium reaches
93.8%。
Claims (8)
1. it is a kind of using coal ash for manufacturing for the method for crystalline sulfuric acid aluminium, characterized by the following steps:
Iron removal by magnetic separation: the first step after flyash mechanical lapping, carries out iron removal by magnetic separation, obtains the flyash except iron；
Second step, sulfuric acid self-heating press acidleach certainly: flyash and water being mixed in proportion, obtain mixture, in proportion by the concentrated sulfuric acid
It is added portionwise into mixture, carries out acid-leaching reaction, obtain mixed solution；
Third step is separated by solid-liquid separation: after acid-leaching reaction is complete, the water that temperature is greater than 80 DEG C is proportionally added into mixed solution, is taken advantage of
Heat is separated by solid-liquid separation, and is obtained aluminum sulfate leachate and be can be used as the leached mud of cement admixture；
4th step, leachate is adjusted and self-heating is concentrated by evaporation: added into aluminum sulfate leachate aluminium hydroxide be adjusted to 1 to pH ~
4, while obtaining the aluminum sulfate concentrate by being evaporated concentration using exothermic heat of reaction；
5th step, crystallisation by cooling: by aluminum sulfate concentrate crystallisation by cooling, obtaining crystalline sulfuric acid aluminium, and aluminum sulfate production is obtained after crushing
Product.
2. it is according to claim 1 it is a kind of using coal ash for manufacturing for the method for crystalline sulfuric acid aluminium, it is characterised in that: the first step
Described in partial size after flyash mechanical lapping be 100 ~ 400 mesh.
3. it is according to claim 1 it is a kind of using coal ash for manufacturing for the method for crystalline sulfuric acid aluminium, it is characterised in that: second step
Described in sulfuric acid self-heating carried out in enamel glass reaction kettle from pressure acidleach, the mass ratio of flyash and water is 1:0.5 ~ 1:3, dense
The mass ratio of sulfuric acid and flyash is 0.5:1 ~ 5:1, and the temperature of acid-leaching reaction is 120 ~ 180 DEG C, and pressure is 0.1 ~ 0.6MPa, instead
It is 1 ~ 8h between seasonable.
4. it is according to claim 1 it is a kind of using coal ash for manufacturing for the method for crystalline sulfuric acid aluminium, it is characterised in that: second step
Described in sulfuric acid self-heating carried out in enamel glass reaction kettle from pressure acidleach, the mass ratio of flyash and water is 1:0.6 ~ 1:1.5,
The mass ratio of the concentrated sulfuric acid and flyash is 1:1 ~ 3:1, and the temperature of acid-leaching reaction is 130 ~ 160 DEG C, and pressure is 0.2 ~ 0.4MPa.
5. it is according to claim 1 it is a kind of using coal ash for manufacturing for the method for crystalline sulfuric acid aluminium, it is characterised in that: third step
The mass ratio of the middle quality that water is added and flyash is 1.25:1 ~ 2:1.
6. it is according to claim 1 it is a kind of using coal ash for manufacturing for the method for crystalline sulfuric acid aluminium, it is characterised in that: third step
Described in separation of solid and liquid method include self-heating sedimentation separation, plate compression separation, vacuum filtration and centrifuge separation in it is any
It is a kind of.
7. it is according to claim 1 it is a kind of using coal ash for manufacturing for the method for crystalline sulfuric acid aluminium, it is characterised in that: the 4th step
Described in add aluminium hydroxide into aluminum sulfate leachate and be adjusted to 2 ~ 3 to pH.
8. it is according to claim 1 it is a kind of using coal ash for manufacturing for the method for crystalline sulfuric acid aluminium, it is characterised in that: the 5th step
Described in 40 DEG C of temperature < of crystallisation by cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811365048.7A CN109336154A (en) | 2018-11-16 | 2018-11-16 | A method of using coal ash for manufacturing for crystalline sulfuric acid aluminium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811365048.7A CN109336154A (en) | 2018-11-16 | 2018-11-16 | A method of using coal ash for manufacturing for crystalline sulfuric acid aluminium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109336154A true CN109336154A (en) | 2019-02-15 |
Family
ID=65315339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811365048.7A Pending CN109336154A (en) | 2018-11-16 | 2018-11-16 | A method of using coal ash for manufacturing for crystalline sulfuric acid aluminium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109336154A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112725842A (en) * | 2020-12-28 | 2021-04-30 | 郑州大学 | Method for preparing aluminum-silicon-based alloy by using fly ash |
| CN114212799A (en) * | 2021-12-21 | 2022-03-22 | 黑龙江省能源环境研究院 | Coal ash pretreatment method for molecular sieve preparation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020299A (en) * | 2010-12-23 | 2011-04-20 | 南京航空航天大学 | Method for producing industrial activated aluminum oxide from pulverized fuel ash |
| CN102815736A (en) * | 2012-08-14 | 2012-12-12 | 衡阳市建衡实业有限公司 | New aluminum sulfate production process with characteristics of energy saving and quality improvement |
-
2018
- 2018-11-16 CN CN201811365048.7A patent/CN109336154A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020299A (en) * | 2010-12-23 | 2011-04-20 | 南京航空航天大学 | Method for producing industrial activated aluminum oxide from pulverized fuel ash |
| CN102815736A (en) * | 2012-08-14 | 2012-12-12 | 衡阳市建衡实业有限公司 | New aluminum sulfate production process with characteristics of energy saving and quality improvement |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112725842A (en) * | 2020-12-28 | 2021-04-30 | 郑州大学 | Method for preparing aluminum-silicon-based alloy by using fly ash |
| CN114212799A (en) * | 2021-12-21 | 2022-03-22 | 黑龙江省能源环境研究院 | Coal ash pretreatment method for molecular sieve preparation |
| CN114212799B (en) * | 2021-12-21 | 2024-03-12 | 黑龙江省能源环境研究院 | Fly ash pretreatment method for molecular sieve preparation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104495899B (en) | A kind of carbide slag and flyash work in coordination with the method for recycling | |
| CN104016393B (en) | A kind of by dolomite for light calcium carbonate and method of magnesium oxide | |
| CN104445311B (en) | Clean poly-generation preparation method for flyash with high-content silicon dioxide | |
| CN101792187B (en) | Method for producing feed grade ferrous sulfate monohydrate from titanium pigment waste acid condensed slag | |
| CN103101935B (en) | Method for preparing lithium carbonate from coal ash | |
| CN102674409B (en) | Method for preparing rod-like magnesium hydroxide from salt lake brine | |
| CN102020299B (en) | Method for producing industrial activated aluminum oxide from pulverized fuel ash | |
| CN103145160B (en) | Method for producing alumina by using high-alumina fly ash | |
| CN101234774B (en) | Method for preparing aluminum oxide from coal series kaolinite rock or coal gangue | |
| CN115321563B (en) | Method for producing battery grade lithium carbonate by nitric acid pressure leaching of lithium stilbite | |
| CN102897810A (en) | Method for producing aluminum oxide by using fly ash | |
| CN110526263A (en) | A kind of method that aluminium base richness lithium slag prepares lithium carbonate | |
| CN103276218A (en) | Method for recycling vanadium from vanadium-containing electrolysis aluminum slag ash | |
| CN105800653A (en) | Method for extracting aluminum oxide from fly ash on basis of soda-lime sintering process | |
| CN109336154A (en) | A method of using coal ash for manufacturing for crystalline sulfuric acid aluminium | |
| CN109384254A (en) | The method that crystal aluminum chloride and white carbon black are prepared by flyash or gangue | |
| CN103408043B (en) | Method for preparing high-purity magnesium oxide with serpentine as raw material | |
| CN111534704A (en) | Method for synergistically extracting potassium and rubidium from potassium-containing rock | |
| CN108677006A (en) | A method of extracting rubidium chloride from Kaolin Tailings | |
| CN103738972A (en) | Method for preparing silicon micropowder by using pulverized fuel ash aluminum extraction residues | |
| CN108285975B (en) | A kind of method for extracting lithium from lepidolite by using PVC pyrolysis | |
| CN101880772B (en) | Method for recycling magnesium from magnesium-containing waste solution | |
| CN110550646A (en) | preparation method of cesium sulfate and rubidium sulfate | |
| CN110195159A (en) | A kind of method that spodumene prepares alusil alloy and enriching lithium | |
| CN102153118A (en) | Method for producing metallurgical-grade aluminum oxide by using iron-containing aluminum chloride solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190215 |