CN102205982A - Method for recycling acid in process of producing aluminum oxide by using fly ash acid method - Google Patents
Method for recycling acid in process of producing aluminum oxide by using fly ash acid method Download PDFInfo
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- CN102205982A CN102205982A CN 201110103721 CN201110103721A CN102205982A CN 102205982 A CN102205982 A CN 102205982A CN 201110103721 CN201110103721 CN 201110103721 CN 201110103721 A CN201110103721 A CN 201110103721A CN 102205982 A CN102205982 A CN 102205982A
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- flyash
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- 239000002253 acid Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000010881 fly ash Substances 0.000 title claims abstract description 23
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004064 recycling Methods 0.000 title abstract 4
- QPILZZVXGUNELN-UHFFFAOYSA-N sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-N 0.000 title abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000007789 gas Substances 0.000 claims abstract description 24
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 22
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 38
- 238000010521 absorption reaction Methods 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 238000007885 magnetic separation Methods 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000006698 induction Effects 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000006148 magnetic separator Substances 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 239000010883 coal ash Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000012738 dissolution medium Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for recycling acid in a process of producing aluminum oxide by using a fly ash acid method. The method comprises the following steps of: removing iron by magnetically separating fly ash; dissolving in acid; removing the iron by performing resin adsorption; concentrating and crystallizing; calcining; cooling and preliminarily recycling hydrogen chloride gas; secondarily recycling the hydrogen chloride gas; adjusting the concentration of recycled hydrochloric acid; and applying the obtained hydrochloric acid to the step of dissolving in acid. The method has the beneficial effects that: the process is simple, the production process is easily controlled, the production cost is low, and the absorbed hydrogen chloride product can be recycled.
Description
Technical field
The present invention relates to a kind of flyash acid system and produce sour cyclic utilization method in the alumina process.
Background technology
China is big coal country, with coal as the basic fuel of electrical production.The stable development of energy industry in recent years, the rapid increase that has brought the flyash quantity discharged causes huge pressure to Chinese national economy construction and ecotope.Owing to contain valuable mineral resources such as aluminum oxide in the flyash, therefore the fine coal ashes being fully utilized, turns waste into wealth has become extensive studies focus content.Flyash extracts in the method for alumina, and acid system or using acid and alkali combination method just day by day are widely adopted because of it extracts digesting efficiency of alumina height and technology characteristic of simple.Wherein the hydrochloric acid that technical process is produced carries out reusable edible research very high using value, can promote economic cycle development, realizes the efficient utilization of resource.
Acid system or using acid and alkali combination method prepare the recovery problem that unavoidably has hydrochloric acid in the alumina technology and exist from flyash.
CN1792802A discloses " a kind of method of alumina of extracting " from flyash, flyash and the sulfuric acid reaction of this method after with roasting, filter, concentrate generation crystalline sulfuric acid aluminium, again generation aluminum oxide and sulfur trioxide gas are decomposed in the high-temperature calcination of crystalline sulfuric acid aluminium.
CN101234774A discloses " a kind of prepare method of alumina by coal series kaolin rock or coal gangue ", this method is calcining and activating behind fragmentation, grinding with coal series kaolin rock or coal gangue, generate liquor alumini chloridi with hydrochloric acid reaction then, by salting-out process crystal aluminum chloride is settled out and separates, the crystal aluminum chloride calcining and decomposing generates aluminum oxide and hydrogen chloride gas.
CN1065255A discloses a kind of " technique for production of alumina by chlorhydric acid-soda method ", is dissolution medium with hydrochloric acid in the technology, and ore Cheng Fenhou in small, broken bits through high-temperature roasting, with salt and hcl reaction, generates alkaline aluminium salt, through separating desiliconization in the high pressure enamel reaction still.Alkaline aluminium salt evaporation concentration, roasting decomposition are made γ shape aluminum oxide and hydrogen chloride gas.Above patent is not all launched further experimental study to the acid recovery aspect, just simple the introduction.
Summary of the invention
The purpose of this invention is to provide sour cyclic utilization method in a kind of circulating fluid bed coal ash acid system production metallurgy grade aluminum oxide process.Method of the present invention may further comprise the steps:
1, magnetically separating and removing ion from fly ash: the fluid bed powder coal ash is looked its granularity, reach below 100 orders through pulverizing, adding water, to be made into solid content be that 20～40wt%, preferable range are the slurry of 30～35wt%, on upright ring type magnetic separator, carry out magnetic separation, magnetic separation field intensity 1.0～2.0 ten thousand GS, preferable range are 1.5～1.75 ten thousand GS, according to the difference of iron level in the flyash, this process can repeat, and the iron oxide content in ash is reduced to (in ferric oxide) below the 1.0wt%.Slurry after the magnetic separation obtains solid content after solid-liquid separation be that 25～50wt%, preferable range are the filter cake of 30～45wt%.
2, acid is molten: it is molten to place acid-resistant reacting kettle to carry out hydrochloric acid acid the filter cake after the magnetic separation, concentration of hydrochloric acid is 20～30wt%, in the hydrochloric acid in HCl and the flyash mol ratio of aluminum oxide be that 4: 1～9: 1, preferable range are 4.5: 1～6: 1, the stripping temperature is that 100 ℃～200 ℃, preferable range are 130 ℃～150 ℃, stripping pressure 0.1～2.5MPa, preferable range are 0.3～1.0MPa, and dissolution time is that 0.5h～4h, preferable range are 1.5h～2.5h; Acid is molten after solid-liquid separation obtains liquor alumini chloridi.
3, resin absorption: the liquor alumini chloridi feeding is equipped with in the resin column of macroporous type resin cation (R.C.), utilizes resin that the adsorptive power of iron is carried out deironing, obtain refined crystalline aluminium chloride liquid.Treatment temp is that room temperature～90 ℃, preferable range are 60 ℃～80 ℃ during absorption, the liquor alumini chloridi flow velocity be 1～4 times of resin volume/hour, preferable range be 2～3 times of resin volumes/hour.Resin column can adopt the mode of single-column or twin columns polyphone.Resin is preferably D001,732,742,7020H, 7120H, JK008 or SPC-1 resin etc.
4, condensing crystal: refined crystalline aluminium chloride liquid is-0.03 at pressure～-0.07MPa, preferable range be-0.04～-0.06MPa, temperature is that 50～110 ℃, preferable range are condensing crystal under 70～80 ℃ the condition, obtain the crystal aluminum chloride crystal, the crystal weight that concentrated time control makes accounts for 40～65% of former refined crystalline aluminium chloride liquid weight.
5, calcining: crystal aluminum chloride calcine the preparation aluminum oxide in having the High Temperature Furnaces Heating Apparatus of gas concentration unit: crystal aluminum chloride is 950～1100 ℃ at 900～1200 ℃, preferable range calcined 1～4 hour, or earlier with crystal aluminum chloride 300～500 ℃ of thermal degradation 1～2 hour, be warming up to 900～1200 ℃ of calcinings 1～3 hour then, obtain alumina product after the thermolysis and produce hydrogen chloride gas.
6, hydrogen chloride gas is cooled to below 100 ℃ by cooling tower, enter in the acid absorption column, water flow jet speed is 100～120L/min in the control acid absorption column, carries out acid gas and tentatively reclaims.
7, the acid gas that does not absorb fully in the absorption tower is imported in the vacuum cycle acid storage tank, control its vacuum tightness and be-0.05～-0.07KPa carries out the secondary recovery of hydrochloric acid.
8, emit absorbing acid in absorption tower and the acid storage tank, add the concentrated hydrochloric acid that entry or concentration are 37wt% in proportion, regulating its concentration is 20～30wt%, returns the sour molten step in the 2nd step.
As preferred implementation, the upright ring type magnetic separator that the inventive method is used number is a disclosed upright ring type magnetic separator in 201010112520.3 as Chinese patent application, and the structure of upright ring type magnetic separator comprises: change, induction medium, upper yoke, lower yoke, magnet coil, opening for feed, mine tailing bucket and flushometer.Wherein, induction medium is installed in the change, magnet coil is arranged on around upper yoke and the lower yoke, so that upper yoke and lower yoke become a pair of generation vertical direction field pole, described upper yoke and lower yoke are separately positioned on interior, the outer both sides of ring of ring of change below, wherein, described induction medium is the Composite Steel expanded metals, every layer of expanded metal lath weaved into by the silk stalk, the edge of described silk stalk has rib shape wedge angle, described upper yoke is connected with opening for feed, and described lower yoke is connected with the mine tailing bucket that is used for discharging, and described flushometer is positioned at the change top.
Usefulness of the present invention is that technology is simple, and production process is easy to control, production cost is low, the hydrogenchloride product reusable edible of absorption.By method of the present invention, the cyclic utilization rate of hydrogenchloride can reach more than 99.5%.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.
The upright ring type magnetic separator structural representation that Fig. 2 uses for the present invention.
Embodiment
Raw material adopts certain heat power plant's output circulating fluid bed coal ash, and its chemical ingredients is as shown in table 1.
Table 1: circulating fluid bed coal ash chemical ingredients (wt%)
| SiO 2 | Al 2O 3 | TiO 2 | CaO | MgO | TFe 2O 3 | FeO | K 2O | Na 2O | LOS | SO 3 | Summation |
| 34.5 | 47.28 | 1.5 | 3.59 | 0.25 | 1.57 | 0.24 | 0.41 | 0.19 | 6.77 | 1.32 | 96.3 |
The structure of upright ring type magnetic separator used in the present invention comprises: change 101, induction medium 102, upper yoke 103, lower yoke 104, magnet coil 105, opening for feed 106, mine tailing bucket 107 and flushometer 108.Wherein, induction medium 102 is installed in the change 101, magnet coil 105 is arranged on around upper yoke 103 and the lower yoke 104, so that upper yoke 103 and lower yoke 104 become a pair of generation vertical direction field pole, described upper yoke 103 and lower yoke 104 are separately positioned in the ring of change 101 belows, encircle outer both sides, wherein, described induction medium 102 is the Composite Steel expanded metals, every layer of expanded metal lath weaved into by the silk stalk, the edge of described silk stalk has rib shape wedge angle, described upper yoke 103 is connected with opening for feed 106, and described lower yoke 104 is connected with the mine tailing bucket 107 that is used for discharging, and described flushometer 108 is positioned at change 101 tops.
Embodiment 1
Get the fluid bed powder coal ash and reach 150 orders, add water and make the slurry that contains admittedly for 30wt% through pulverizing, magnetic separation on upright ring type magnetic separator, magnetic separation field intensity 1.5 ten thousand Gs, magnetic separation three times, iron oxide content is 0.8wt% in flyash.With the filter cake that is contained admittedly after the press filtration of plate basket pressure filter for 34.5wt%.Filter cake is put into acid-resistant reacting kettle, and it is molten that the hydrochloric acid that adds 22wt% carries out acid, in the hydrochloric acid in HCl and the ash mol ratio of aluminum oxide be 5: 1,150 ℃ of temperature of reaction, in 2 hours reaction times, reaction pressure is 1.0MPa.Will the acid molten liquor alumini chloridi that obtains feeds in the resin column and carries out deironing, and resin column is in the single-column mode, and the resin of employing is D001 (Wan Dong chemical plant, Anhui), and treatment temp is 60 ℃, the liquor alumini chloridi flow velocity be 3 times of resin volumes/hour.The refined crystalline aluminium chloride liquid that generates sent into carry out evaporation concentration in the concentration tank, concentrate pressure-0.05MPa, 80 ℃ of thickening temperatures, control crystalline weight accounts for 50% of former refined crystalline aluminium chloride liquid weight, obtains crystal aluminum chloride.Crystal aluminum chloride is decomposed into aluminum oxide at 400 ℃, 2 hours resolving times, change High Temperature Furnaces Heating Apparatus then over to, and calcine down at 1100 ℃ and obtained alumina product in 2 hours.
The hydrogen chloride gas that calcining generates cools to 98 ℃ by cooling tower, enters in the acid absorption column.Water flow jet speed is 100L/min in the control acid absorption column, carries out acid gas and tentatively reclaims.The acid gas that does not absorb fully in the absorption tower is imported in the vacuum cycle acid storage tank, control its vacuum tightness and carry out the secondary recovery of hydrochloric acid for-0.05KPa.Acid is absorbed liquid weigh and chemical analysis, obtaining concentration of hydrochloric acid is 23.5wt%, and the recovery of hydrogen chloride rate is 99.65%.Emit absorbing acid in absorption tower and the acid storage tank at last, adding water, to regulate its concentration be 22wt%, returns sour molten step.
Embodiment 2
Prepare the main technique condition of metallurgical-grade aluminum oxide with embodiment 1 with the circulating fluidized bed ash.It is 26.5wt% that wherein sour molten step adds concentration of hydrochloric acid.
The hydrogen chloride gas that calcining generates cools to 90 ℃ by cooling tower, enters in the acid absorption column, and water flow jet speed is that 120L/min carries out acid gas and tentatively reclaims in the control acid absorption column.The acid gas that does not absorb fully in the absorption tower is imported in the vacuum cycle acid storage tank, control its vacuum tightness and carry out the secondary recovery of hydrochloric acid for-0.07KPa.Acid is absorbed liquid weigh and chemical analysis, obtaining concentration of hydrochloric acid is 26.9wt%, and the recovery of hydrogen chloride rate is 99.75%.At last, emit absorbing acid in absorption tower and the acid storage tank, adding water, to regulate its concentration be 26.5wt%, returns sour molten step.
Embodiment 3
With embodiment 1, it is 30wt% that wherein sour molten step adds concentration of hydrochloric acid with the grey main technique condition for preparing aluminum oxide of circulating fluidized bed.
The hydrogen chloride gas that calcining generates cools to 94 ℃ by cooling tower, enters in the acid absorption column, and water flow jet speed is that 110L/min carries out acid gas and tentatively reclaims in the control acid absorption column.The acid gas that does not absorb fully in the absorption tower is imported in the vacuum cycle acid storage tank, control its vacuum tightness and carry out the secondary recovery of hydrochloric acid for-0.06KPa.Acid is absorbed liquid weigh and chemical analysis, obtaining concentration of hydrochloric acid is 25.4wt%, and the recovery of hydrogen chloride rate is 99.69%.At last, emit absorbing acid in absorption tower and the acid storage tank, it is 30wt% that the hydrochloric acid that adds concentration and be 37wt% is regulated its concentration, returns sour molten step.
Claims (10)
1. a flyash acid system is produced sour cyclic utilization method in the alumina process, comprising:
1), magnetically separating and removing ion from fly ash: flyash reaches below 100 orders through pulverizing, and the slurry that add water to be made into solid content be 20～40wt%, is preferably 30～35wt% carries out magnetic separation, magnetic separation field intensity 1.0～2.0 ten thousand GS on upright ring type magnetic separator; The filter cake that slurry after the magnetic separation obtains solid content after solid-liquid separation is 25～50wt%, be preferably 30～45wt%;
2), acid is molten: it is molten to place acid-resistant reacting kettle to carry out hydrochloric acid acid the filter cake after the magnetic separation, concentration of hydrochloric acid is 20～30wt%, in the hydrochloric acid in HCl and the flyash mol ratio of aluminum oxide be 4: 1～9: 1, the stripping temperature is 100 ℃～200 ℃, is preferably 130 ℃～150 ℃, stripping pressure 0.1～2.5MPa, be preferably 0.3～1.0MPa, dissolution time is 0.5h～4h, be preferably 1.5h～2.5h; Acid is molten after solid-liquid separation obtains liquor alumini chloridi;
3), resin absorption: liquor alumini chloridi is fed deironing in the resin column that the macroporous type resin cation (R.C.) is housed, obtain refined crystalline aluminium chloride liquid, treatment temp is room temperature～90 ℃, is preferably 60 ℃～80 ℃, the liquor alumini chloridi flow velocity be 1～4 times of resin volume/hour, be preferably 2～3 times of resin volumes/hour;
4), condensing crystal: refined crystalline aluminium chloride liquid is-0.03 at pressure～-0.07MPa, be preferably-0.04～-0.06MPa, temperature is 50～110 ℃, be preferably condensing crystal under 70～80 ℃ the condition, obtains the crystal aluminum chloride crystal;
5), calcining: crystal aluminum chloride was calcined 1～4 hour down at 900～1200 ℃, obtained alumina product and produce hydrogen chloride gas;
6), hydrogen chloride gas is cooled to below 100 ℃ by cooling tower, enter in the acid absorption column, water flow jet speed is 100～120L/min in the control acid absorption column, carries out acid gas and tentatively reclaims;
7), unabsorbed acid gas in the absorption tower is imported in the vacuum cycle acid storage tank, control its vacuum tightness and be-0.05～-0.07KPa, carry out the secondary recovery of hydrochloric acid;
8), emit absorbing acid in absorption tower and the acid storage tank, add the concentrated hydrochloric acid that entry or concentration are 37wt% in proportion, regulating its concentration is 20～30wt%, returns the 2nd) step acid is molten.
2. method according to claim 1 is characterized in that, the field intensity of magnetic separation described in the step 1) is 1.5～1.75 ten thousand GS.
3. method according to claim 1 and 2 is characterized in that, after the magnetically separating and removing ion from fly ash step, the content in the ferric oxide of ferric oxide in the flyash is lower than 1.0wt%.
4. method according to claim 1 and 2, it is characterized in that, employed upright ring type magnetic separator in the magnetically separating and removing ion from fly ash step, its structure comprises: change, induction medium, upper yoke, lower yoke, magnet coil, opening for feed, mine tailing bucket and flushometer; Wherein, induction medium is installed in the change, magnet coil is arranged on around upper yoke and the lower yoke, so that upper yoke and lower yoke become a pair of generation vertical direction field pole, described upper yoke and lower yoke are separately positioned on interior, the outer both sides of ring of ring of change below, wherein, described induction medium is the Composite Steel expanded metals, every layer of expanded metal lath weaved into by the silk stalk, the edge of described silk stalk has rib shape wedge angle, described upper yoke is connected with opening for feed, and described lower yoke is connected with the mine tailing bucket that is used for discharging, and described flushometer is positioned at the change top.
5. method according to claim 1 is characterized in that step 2) in the hydrochloric acid in HCl and the flyash mol ratio of aluminum oxide be 4.5: 1～6: 1.
6. method according to claim 1 is characterized in that, described resin column adopts single-column or twin columns series system.
7. method according to claim 1 is characterized in that, described resin is D001,732,742,7020H, 7120H, JK008 or SPC-1 resin.
8. method according to claim 1 is characterized in that, the calcining temperature of step 5) is 950～1100 ℃.
9. method according to claim 1 is characterized in that, step 5) be with crystal aluminum chloride 300～500 ℃ of thermal degradation 1～2 hour, be warming up to 900～1200 ℃ of calcinings 1～3 hour then, obtain alumina product and produce hydrogen chloride gas.
10. method according to claim 1 is characterized in that, crystal weight is 40～65% of a former refined crystalline aluminium chloride liquid weight behind the condensing crystal.
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| CN 201010161865 CN101863498A (en) | 2010-04-27 | 2010-04-27 | Method for recycling acid in process of producing alumina from fly ash by acid method |
| CN 201110103721 CN102205982B (en) | 2010-04-27 | 2011-04-25 | Method for recycling acid in process of producing aluminum oxide by using fly ash acid method |
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| CN110342554A (en) * | 2018-04-03 | 2019-10-18 | 国家能源投资集团有限责任公司 | The method of flyash extraction aluminum and coproducing lithium carbonate |
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| CN101811712A (en) | 2010-04-27 | 2010-08-25 | 中国神华能源股份有限公司 | Method for preparing metallurgical-grade aluminum oxide by using fluid-bed fly ash |
| CN103303948A (en) * | 2012-03-16 | 2013-09-18 | 西安航天动力试验技术研究所 | Impurity removal method in process of preparing alumina from fly ash by using acid method |
| CN103449483A (en) * | 2012-05-29 | 2013-12-18 | 西安航天动力试验技术研究所 | Impurity removing method in process of preparing alumina from fly ash by utilizing acid method |
| CN103449487A (en) * | 2012-05-29 | 2013-12-18 | 西安航天动力试验技术研究所 | Impurity removing method in process of preparing alumina from fly ash by using acid method |
| CN104628019A (en) * | 2013-11-15 | 2015-05-20 | 李进凯 | Method for separating and recovering aluminum oxide form coal ash |
| CN103738990B (en) * | 2013-12-17 | 2015-09-09 | 中国神华能源股份有限公司 | A kind of method utilizing crystal aluminum chloride to produce aluminum oxide |
| AT515557B1 (en) * | 2014-05-28 | 2015-10-15 | Andritz Ag Maschf | Process for the preparation of packaging material |
| CN106966415A (en) * | 2017-03-29 | 2017-07-21 | 西安航天动力试验技术研究所 | The process of aluminum oxide in a kind of acidity extraction coal-powder boiler flyash |
| CN110963515B (en) * | 2019-12-27 | 2021-09-10 | 四川顺应动力电池材料有限公司 | Method for recovering alumina from fly ash |
| CN111620358A (en) * | 2020-05-14 | 2020-09-04 | 江西鹏腾实业有限公司 | Preparation method of high-purity white crystalline aluminum chloride |
| CN112811468B (en) * | 2020-12-25 | 2023-05-23 | 四川省绵阳市华意达化工有限公司 | Method for improving quality of chromic anhydride |
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| CN101863498A (en) | 2010-10-20 |
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