CN103539182B - Method for preparing aluminum chloride hexahydrate by using pulverized fuel ash as raw material through ferrous chloride induced crystallization - Google Patents
Method for preparing aluminum chloride hexahydrate by using pulverized fuel ash as raw material through ferrous chloride induced crystallization Download PDFInfo
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- aluminum chloride
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- iron protochloride
- hydrochloric acid
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Abstract
The invention provides a method for preparing aluminum chloride hexahydrate by using pulverized fuel ash as a raw material through ferrous chloride induced crystallization. The method comprises the following steps: (1) batching the pulverized fuel ash and hydrochloric acid in proportions, and reacting for 1-4 hours at the temperature of 80-120 DEG C; (2) filtering leach liquor and solids, and washing more than three times by using diluted hydrochloric acid; (3) adding a reducing agent to a solution till the electromotive force of the solution is about 770mV, so that all Fe<3+> in the solution is reduced to Fe<2+>, and meanwhile, intrinsic Fe<2+> in the solution generates ferric oxide; (4) adding ferrous chloride, carrying out induction fractal crystallization at the temperature of 80-120 DEG C, filtering to obtain aluminum chloride hexahydrate crystals with relatively good crystalline form, or recrystallizing the obtained crystals, then washing by using a high-concentration aluminium chloride solution, and drying to obtain an aluminum chloride hexahydrate product; (5) adding water, cooling and crystallizing so as to respectively remove calcium, magnesium, potassium, sodium and the like in the solution, and separating out ferrous chloride tetrahydrate (FeC12.4H2O); and (6) carrying out a hydrothermal reaction for 4-12 hours at the temperature of 120-200 DEG C by using obtained the ferrous chloride tetrahydrate, and reacting so as to generate ferric oxide and an HCI solution. The method is easy to operate, pollution-free to environments and in line with the requirements of green chemical industries on clean production.
Description
Technical field
The present invention relates to the utilization of fly ash, relate to a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate particularly.
Background technology
Flyash is one of industrial residue that China's current emissions amount is larger, nearly 5,000 ten thousand tons of China present stage, bed drain purge year.To 2012, its total emission volumn nearly 500,000,000 tons, this caused immense pressure to the development of the national economy of China and ecotope.But containing a large amount of utilizable Al in flyash
2o
3(~ 40%wt) and SiO
2resource, therefore has great application prospect.
The method extracting aluminium both at home and abroad from flyash can be divided into alkaline process and acid system.Alkaline process has very ripe industrial application for process is high-grade containing bauxite resource, but due to the SiO in flyash
2content higher (Al/Si≤1), causes more silicon to be dissolved in alkali lye, thus causes the loss of alkali, therefore can not extract aluminium wherein with traditional bayer process.Compared with alkaline process, utilize acid system silicon-dioxide can be avoided to be dissolved in leach liquor to extract bauxite resource, and new solid residue can not be produced during the course.Have acidity extraction bauxite resource both at home and abroad and study widely, the acid of use mostly is hydrochloric acid or sulfuric acid etc., and what have prospects for commercial application most is hydrochloric acid method.United States Bureau of Mines once utilized the aluminium in hydrochloric acid extraction clay (composition and flyash similar) and then prepared aluminum oxide and carried out a series of research, and had carried out shop test.In its flow process, the hydrochloric acid of 26% of the clay after calcining carries out acidleach, and the solvent-extracted method of the soln using after acidleach is by Fe
3+removing, the mother liquor after removal of impurities utilizes the method for evaporation by AlCl
3solution concentrate, then in this solution, passing into HCl gas to concentration of hydrochloric acid is 36%, and Aluminum Chloride Hexahydrate can most of crystallization.
It should be noted that this technique also also exists some shortcomings: (1) utilizes solvent-extracted method to remove Fe
3+, process complexity is loaded down with trivial details, and solvent load is large, and cost is also higher; (2) utilize HCl gas to make Aluminum Chloride Hexahydrate crystallization, operational condition is harsh, and corrodibility is large, higher to equipment requirements, and easily causes environmental pollution.Therefore need to seek the bauxite resource that new method is come in extract powder coal ash.
Summary of the invention
The technology of the present invention is dealt with problems: overcome the deficiencies in the prior art, there is provided a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate, the method easy handling, and low for equipment requirements, environmentally safe, meets the requirement of green chemical industry to cleaner production.
Technical solution of the present invention: a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate, comprises the following steps:
(1) leach: be that the hydrochloric acid of 26 ~ 30% is according to 1:(1.05 ~ 1.20 by flyash and mass concentration) ratio prepare burden, react under temperature of reaction 80 ~ 120 ° of C, reaction times 1 ~ 4h, obtains leach liquor and solid;
(2) filtration washing: described leach liquor and solid are filtered, obtain filtrate and filter residue, adopt dilute hydrochloric acid washings to wash described filter residue more than three times, mix as stock solution using described filtrate with described dilute hydrochloric acid washings, the filter residue after described washing is as brick-making raw material;
(3) reduce: in stock solution described in step (2), add reductive agent make the electromotive force of this solution reach 770mV, now Fe in stock solution
3+restore All becomes Fe
2+, obtain the stock solution after reducing; By the stock solution after reduction together with Fe original in stock solution
2+perform step (6) and generate ferric oxide to remove;
(4) fractal crystallization is induced: add iron protochloride and carry out inducing fractal crystallization under 80 ~ 120 ° of C in the stock solution of step (3) after reduction, utilize common-ion effect, under the prerequisite controlling water evaporation quantity, remove calcium, magnesium, potassium, sodium and iron contamination by crystallization, obtain the good Aluminum Chloride Hexahydrate crystal of crystalline form; The crystal obtained after filtration or after recrystallization with closely saturated liquor alumini chloridi carry out washing and drying, namely obtain Aluminum Chloride Hexahydrate solid phase prod;
(5) decrease temperature crystalline: the iron protochloride in the filtrate that step (4) obtains after filtering can recycle, calcium in filtrate, magnesium, potassium and sodium impurity by add water and decrease temperature crystalline operation to remove respectively, the iron protochloride concentration in circulation fluid is also by add water and cooling operation keeps constant to separate out four water iron protochloride crystal;
(6) be oxidized: four water iron protochlorides step (5) obtained carry out hydro-thermal reaction, reaction times 4 ~ 12h under temperature of reaction 120 ~ 200 ° of C, reaction generates ferric oxide and hydrochloric acid soln; Ferric oxide makes pigment or coating, and HCl recovery recycles.
In described step (1), flyash and concentration are the ratio of components of the hydrochloric acid of 26 ~ 30% is 1:(1.05 ~ 1.10).
In described step (1), temperature of reaction is 100 ~ 110 ° of C.
In described step (1), the reaction times is 1 ~ 2h.
The mass concentration of the dilute hydrochloric acid in described step (2) is 0.1%.
Reductive agent in described step (3) is iron filings.
In described step (4), the add-on of iron protochloride is 5 ~ 20% of the aluminum chloride molar weight contained in solution.
In described step (5), the add-on of water is 5 ~ 40% of water content in step (4) filtrate.
In described step (6), temperature of reaction is 150 ~ 180 ° of C.
In described step (6), the reaction times is 6 ~ 10h.
Principal reaction mechanism involved in the present invention is as follows:
Leaching workshop section: Al
2o
3(s)+6HCl (aq) → 2AlCl
3(aq)+3H
2o
Reduction workshop section: 2FeCl
3(aq)+Fe → 3FeCl
2(aq)
Oxidation section: 4FeCl
2(aq)+O
2+ 4H
2o (l) → 2Fe
2o
3(s)+8HCl (aq)
The phasor of aluminum chloride-iron protochloride-aqueous systems involved in the present invention and typical crystallization operation process are as shown in Figure 2.The common saturation point of aluminum chloride-iron protochloride when point E, B are respectively 25 ° of C and 90 ° of C.Under 90 ° of C, induce fractal crystallization (pilot wire is AB) to the solution in step 3), when solution evaporation is to B point, the solid of now separating out is Aluminum Chloride Hexahydrate.In order to crystallization goes out iron protochloride, now need to add a small amount of water and make strength of solution be down to D point (can not more than C point), then decrease temperature crystalline (pilot wire is DE) is carried out to solution.Like this, the solid of precipitation is four water iron protochloride (FeCl
24H
2o).
The present invention's advantage is compared with prior art:
(1) present invention achieves the higher value application of flyash.While preparing Aluminum Chloride Hexahydrate, the tailings produced in process as brick producing material, can improve economic benefit.Whole technical process environmental protection, environmentally friendly, meet the requirement of Sustainable development.
(2) the present invention utilizes iron protochloride as circulatory mediator, the method of the fractal crystallization of induction is adopted to separate out Aluminum Chloride Hexahydrate, solve the pollution and high energy consumption problem that use HCl gas crystal aluminum chloride workshop section to produce, simultaneously because the corrodibility of circulatory mediator is less, also reduce the requirement to crystallizer.
(3) the present invention adopts redox method to remove the iron in flyash, eliminates the workshop section utilizing solvent extraction deironing.Take hydrothermal method to be oxidized iron protochloride, the ferric oxide of generation can be used as pigment or coating, and can recycle by recovery part HCl, therefore also reduces process costs.
Accompanying drawing explanation
Fig. 1 is a kind of process flow sheet taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate of the present invention;
Fig. 2 is the phasor of aluminum chloride-iron protochloride-aqueous systems involved in the present invention and typical crystallization operation schematic diagram.
Embodiment
The present invention is introduced in detail below in conjunction with drawings and the specific embodiments.But following embodiment is only limitted to explain the present invention, and protection scope of the present invention should comprise the full content of claim, is not limited only to the present embodiment.
Embodiment 1
The hydrochloric acid soln of certain flyash (composition is in table 1) 500g and 26% is prepared burden in the ratio of 1:1.05, is placed in the 4L glass reaction still being furnished with prolong, under 80 ° of C, reacts 4h.After having reacted, filtered by leaching liquid, the salt acid elution more than three times of 0.1% of the filter residue after filtration, collects filter residue for subsequent use as brick-making raw material.Filtrate being mixed with dilute hydrochloric acid washings and add electromotive force in iron filings to solution is 770mV, makes Fe
3+restore All becomes Fe
2+.The FeCl of 0.1 ~ 0.2mol is added to the solution after reduction
2under 80 ° of C, carry out evaporative crystallization, control the amount of transpiring moisture, make the crystal of precipitation be Aluminum Chloride Hexahydrate.Carry out solid-liquid separation by filtering, the crystal obtained washs more than three times with closely saturated liquor alumini chloridi after recrystallization, is then placed in 95 ° of C drying 12 ~ 24h.
Certain flyash composition of table 1., wt%
Detect through chemical analysis and XRD and analyze, in single cycle, the yield of Al is 21.6%, and the purity of Aluminum Chloride Hexahydrate is 97.0%.
Filtrate enters to be circulated next time, after repeatedly circulation, adopts and adds water and major impurity (calcium, magnesium, potassium, sodium) in the method for decrease temperature crystalline removing circulation fluid, and separate out four water iron protochloride crystal to keep the constant of iron protochloride content in circulation fluid.The iron protochloride obtained carries out hydro-thermal reaction 12h under 120 ° of C, generates ferric oxide and hydrochloric acid soln, collects ferric oxide to make pigment or coating, the recyclable recycling of hydrochloric acid.
Embodiment 2
The hydrochloric acid soln of certain flyash (composition is in table 1) 500g and 28% is prepared burden in the ratio of 1:1.10, is placed in the 4L glass reaction still being furnished with prolong, under 100 ° of C, reacts 2h.After having reacted, filtered by leaching liquid, the salt acid elution more than three times of 0.1% of the filter residue after filtration, collects filter residue for subsequent use as brick-making raw material.Filtrate being mixed with dilute hydrochloric acid washings and add a small amount of iron filings to the electromotive force in solution is 770mV, makes Fe
3+restore All becomes Fe
2+.The FeCl of 0.1 ~ 0.2mol is added to the solution after reduction
2under 90 ° of C, carry out evaporative crystallization, control the amount of transpiring moisture, make the crystal of precipitation be Aluminum Chloride Hexahydrate.Carry out solid-liquid separation by filtering, the crystal obtained washs more than three times with closely saturated liquor alumini chloridi after recrystallization, is then placed in 95 ° of C drying 12 ~ 24h.
Detect through chemical analysis and XRD and analyze, in single cycle, the yield of Al is 20.8%, and the purity of Aluminum Chloride Hexahydrate is 96.2%.
Filtrate enters to be circulated next time, after repeatedly circulation, adopts and adds water and major impurity (calcium, magnesium, potassium, sodium) in the method for decrease temperature crystalline removing circulation fluid, and separate out four water iron protochloride crystal to keep the constant of iron protochloride content in circulation fluid.The iron protochloride obtained carries out hydro-thermal reaction 8h under 160 ° of C, generates ferric oxide and hydrochloric acid soln, collects ferric oxide to make pigment or coating, the recyclable recycling of hydrochloric acid.
Embodiment 3
The hydrochloric acid soln of certain flyash (composition is in table 1) 500g and 30% is prepared burden in the ratio of 1:1.20, is placed in the 4L glass reaction still being furnished with prolong, under 120 ° of C, reacts 1h.After having reacted, filtered by leaching liquid, the salt acid elution more than three times of 0.1% of the filter residue after filtration, collects filter residue for subsequent use as brick-making raw material.Filtrate being mixed with dilute hydrochloric acid washings and add a small amount of iron filings to the electromotive force in solution is 770mV, makes Fe
3+restore All becomes Fe
2+.The FeCl of 0.1 ~ 0.2mol is added to the solution after reduction
2under 110 ° of C, carry out evaporative crystallization, control the amount of transpiring moisture, make the crystal of precipitation be Aluminum Chloride Hexahydrate.Carry out solid-liquid separation by filtering, the crystal obtained washs more than three times with closely saturated liquor alumini chloridi after recrystallization, is then placed in 95 ° of C drying 12 ~ 24h.
Detect through chemical analysis and XRD and analyze, in single cycle, the yield of Al is 20.6%, and the purity of Aluminum Chloride Hexahydrate is 96.3%.
Filtrate enters to be circulated next time, after repeatedly circulation, adopts and adds water and major impurity (calcium, magnesium, potassium, sodium) in the method for decrease temperature crystalline removing circulation fluid, and separate out four water iron protochloride crystal to keep the constant of iron protochloride content in circulation fluid.The iron protochloride obtained carries out hydro-thermal reaction 4h under 200 ° of C, generates ferric oxide and hydrochloric acid soln, collects ferric oxide to make pigment or coating, the recyclable recycling of hydrochloric acid.
Embodiment 4
The hydrochloric acid soln of certain flyash (composition is in table 1) 100kg and 26% is prepared burden in the ratio of 1:1.10, is placed in the 5m of sealing
3in leaching reactor, under 110 ° of C, react 2h.After having reacted, filtered by leaching liquid, the salt acid elution more than three times of 0.1% of the filter residue after filtration, collects filter residue for subsequent use as brick-making raw material.Filtrate being mixed with dilute hydrochloric acid washings and add a small amount of iron filings to the electromotive force in solution is 770mV, makes Fe
3+restore All becomes Fe
2+, be then placed in 5m
3in evaporative crystallizer.The FeCl of about 20mol is added in evaporative crystallizer
2under 90 ° of C, carry out evaporative crystallization, control the amount of transpiring moisture, make the crystal of precipitation be Aluminum Chloride Hexahydrate.Carry out solid-liquid separation by filtering, the crystal obtained washs more than three times with closely saturated liquor alumini chloridi after recrystallization, is then placed in 95 ° of C drying 12 ~ 24h.
Detect through chemical analysis and XRD and analyze, in single cycle, the yield of Al is 20.3%, and the purity of Aluminum Chloride Hexahydrate is 95.8%.
Filtrate enters to be circulated next time, after repeatedly circulation, adopts and adds water and major impurity (calcium, magnesium, potassium, sodium) in the method for decrease temperature crystalline removing circulation fluid, and separate out four water iron protochloride crystal to keep the constant of iron protochloride content in circulation fluid.The iron protochloride obtained carries out hydro-thermal reaction 6h under 180 ° of C, generates ferric oxide and hydrochloric acid soln, collects ferric oxide to make pigment or coating, the recyclable recycling of hydrochloric acid.
Embodiment 5
The hydrochloric acid soln of certain flyash (composition is in table 2) 500g and 26% is prepared burden in the ratio of 1:1.05, is placed in the 4L glass reaction still being furnished with prolong, under 90 ° of C, reacts 3h.After having reacted, filtered by leaching liquid, the salt acid elution more than three times of 0.1% of the filter residue after filtration, collects filter residue for subsequent use as brick-making raw material.Filtrate being mixed with dilute hydrochloric acid washings and add a small amount of iron filings to the electromotive force in solution is 770mV, makes Fe
3+restore All becomes Fe
2+.The FeCl of 0.1 ~ 0.2mol is added to the solution after reduction
2under 120 ° of C, carry out evaporative crystallization, control the amount of transpiring moisture, make the crystal of precipitation be Aluminum Chloride Hexahydrate.Carry out solid-liquid separation by filtering, the crystal obtained washs more than three times with closely saturated liquor alumini chloridi after recrystallization, is then placed in 95 ° of C drying 12 ~ 24h.
Detect through chemical analysis and XRD and analyze, in single cycle, the yield of Al is 21.2%, and the purity of Aluminum Chloride Hexahydrate is 96.5%.
Filtrate enters to be circulated next time, after repeatedly circulation, adopts and adds water and major impurity (calcium, magnesium, potassium, sodium) in the method for decrease temperature crystalline removing circulation fluid, and separate out four water iron protochloride crystal to keep the constant of iron protochloride content in circulation fluid.The iron protochloride obtained carries out hydro-thermal reaction 10h under 140 ° of C, generates ferric oxide and hydrochloric acid soln, collects ferric oxide to make pigment or coating, the recyclable recycling of hydrochloric acid.
Certain flyash composition of table 2., wt%
Embodiment 6
The hydrochloric acid soln of certain flyash (composition is in table 2) 500g and 28% is prepared burden in the ratio of 1:1.10, is placed in the 4L glass reaction still being furnished with prolong, under 100 ° of C, reacts 2h.After having reacted, filtered by leaching liquid, the salt acid elution more than three times of 0.1% of the filter residue after filtration, collects filter residue for subsequent use as brick-making raw material.Filtrate being mixed with dilute hydrochloric acid washings and add a small amount of iron filings to the electromotive force in solution is 770mV, makes Fe
3+restore All becomes Fe
2+.The FeCl of 0.1 ~ 0.2mol is added to the solution after reduction
2under 120 ° of C, carry out evaporative crystallization, control the amount of transpiring moisture, make the crystal of precipitation be Aluminum Chloride Hexahydrate.Carry out solid-liquid separation by filtering, the crystal obtained washs more than three times with closely saturated liquor alumini chloridi after recrystallization, is then placed in 95 ° of C drying 12 ~ 24h.
Detect through chemical analysis and XRD and analyze, in single cycle, the yield of Al is 21.1%, and the purity of Aluminum Chloride Hexahydrate is 97.3%.
Filtrate enters to be circulated next time, after repeatedly circulation, adopts and adds water and major impurity (calcium, magnesium, potassium, sodium) in the method for decrease temperature crystalline removing circulation fluid, and separate out four water iron protochloride crystal to keep the constant of iron protochloride content in circulation fluid.The iron protochloride obtained carries out hydro-thermal reaction 8h under 150 ° of C, generates ferric oxide and hydrochloric acid soln, collects ferric oxide to make pigment or coating, the recyclable recycling of hydrochloric acid.
Embodiment 7
The hydrochloric acid soln of certain flyash (composition is in table 2) 500g and 30% is prepared burden in the ratio of 1:1.20, is placed in the 4L glass reaction still being furnished with prolong, under 110 ° of C, reacts 2h.After having reacted, filtered by leaching liquid, the salt acid elution more than three times of 0.1% of the filter residue after filtration, collects filter residue for subsequent use as brick-making raw material.Filtrate being mixed with dilute hydrochloric acid washings and add a small amount of iron filings to the electromotive force in solution is 770mV, makes Fe
3+restore All becomes Fe
2+.The FeCl of 0.1 ~ 0.2mol is added to the solution after reduction
2under 100 ° of C, carry out evaporative crystallization, control the amount of transpiring moisture, make the crystal of precipitation be Aluminum Chloride Hexahydrate.Carry out solid-liquid separation by filtering, the crystal obtained washs more than three times with closely saturated liquor alumini chloridi after recrystallization, is then placed in 95 ° of C drying 12 ~ 24h.Detect through chemical analysis and XRD and analyze, in single cycle, the yield of Al is 21.5%, and the purity of Aluminum Chloride Hexahydrate is 95.9%.
Filtrate enters to be circulated next time, after repeatedly circulation, adopts and adds water and major impurity (calcium, magnesium, potassium, sodium) in the method for decrease temperature crystalline removing circulation fluid, and separate out four water iron protochloride crystal to keep the constant of iron protochloride content in circulation fluid.The iron protochloride obtained carries out hydro-thermal reaction 5h under 180 ° of C, generates ferric oxide and hydrochloric acid soln, collects ferric oxide to make pigment or coating, the recyclable recycling of hydrochloric acid.
Embodiment 8
The hydrochloric acid soln of certain flyash (composition is in table 2) 100kg and 26% is prepared burden in the ratio of 1:1.10, is placed in the 5m of sealing
3in leaching reactor, under 110 ° of C, react 2h.After having reacted, filtered by leaching liquid, the salt acid elution more than three times of 0.1% of the filter residue after filtration, collects filter residue for subsequent use as brick-making raw material.Filtrate being mixed with dilute hydrochloric acid washings and add a small amount of iron filings to the electromotive force in solution is 770mV, makes Fe
3+restore All becomes Fe
2+, be then placed in 5m
3in evaporative crystallizer.The FeCl of about 20mol is added in evaporative crystallizer
2under 90 ° of C, carry out evaporative crystallization, control the amount of transpiring moisture, make the crystal of precipitation be Aluminum Chloride Hexahydrate.Carry out solid-liquid separation by filtering, the crystal obtained washs more than three times with closely saturated liquor alumini chloridi after recrystallization, is then placed in 95 ° of C drying 12 ~ 24h.
Detect through chemical analysis and XRD and analyze, in single cycle, the yield of Al is 21.4%, and the purity of Aluminum Chloride Hexahydrate is 96.1%.
Filtrate enters to be circulated next time, after repeatedly circulation, adopts and adds water and major impurity (calcium, magnesium, potassium, sodium) in the method for decrease temperature crystalline removing circulation fluid, and separate out four water iron protochloride crystal to keep the constant of iron protochloride content in circulation fluid.The iron protochloride obtained carries out hydro-thermal reaction 7h under 160 ° of C, generates ferric oxide and hydrochloric acid soln, collects ferric oxide to make pigment or coating, the recyclable recycling of hydrochloric acid.
It should be noted that, according to the above embodiment of the present invention, those skilled in the art are the four corners that can realize the claims in the present invention 1 and appurtenance completely, implementation procedure and the same the various embodiments described above of method.
In a word, the novel process using iron protochloride as circulatory mediator induced crystallization Aluminum Chloride Hexahydrate of the present invention's proposition.Utilize redox method iron removal simple to operate in novel process, eliminate the workshop section of complicated solvent extraction deironing.And adopting single vaporization and under controlling the prerequisite of steam output, utilizing common-ion effect can obtain the good Aluminum Chloride Hexahydrate crystal of crystalline form.Whole technological process easy handling, and low for equipment requirements, and environmentally safe, meets the requirement of green chemical industry to cleaner production.
Non-elaborated part of the present invention belongs to the known technology of those skilled in the art.
Claims (10)
1. take flyash as the method that raw material iron protochloride induced crystallization prepares Aluminum Chloride Hexahydrate, it is characterized in that comprising the following steps:
(1) leach: be that the hydrochloric acid of 26 ~ 30% is according to 1:(1.05 ~ 1.20 by flyash and mass concentration) mass ratio prepare burden, react at temperature of reaction 80 ~ 120 DEG C, reaction times 1 ~ 4h, obtain leach liquor and solid;
(2) filtration washing: leach liquor described in step (1) and solid are filtered, obtain filtrate and filter residue, dilute hydrochloric acid washings is adopted to wash described filter residue more than three times, mix as stock solution using described filtrate with described dilute hydrochloric acid washings, the filter residue after described washing is as brick-making raw material;
(3) reduce: in stock solution described in step (2), add reductive agent make the electromotive force of this solution reach 770mV, now Fe in stock solution
3+restore All becomes Fe
2+, obtain the stock solution after reducing; By the stock solution after reduction together with Fe original in stock solution
2+perform step (6) and generate ferric oxide to remove;
(4) fractal crystallization is induced: add iron protochloride and carry out inducing fractal crystallization at 80 ~ 120 DEG C in the stock solution of step (3) after reduction, utilize common-ion effect, under the prerequisite controlling water evaporation quantity, remove calcium, magnesium, potassium, sodium and iron contamination by crystallization, obtain Aluminum Chloride Hexahydrate crystal; The crystal obtained after filtration or after recrystallization with closely saturated liquor alumini chloridi carry out washing and drying, namely obtain Aluminum Chloride Hexahydrate solid phase prod;
(5) decrease temperature crystalline: the iron protochloride in the filtrate that step (4) obtains after filtering can recycle, calcium in filtrate, magnesium, potassium and sodium impurity by add water and decrease temperature crystalline operation to remove respectively, the iron protochloride concentration in circulation fluid also by add water and cooling operation keep constant to separate out four water iron protochloride crystal;
(6) be oxidized: four water iron protochlorides step (5) obtained carry out hydro-thermal reaction, reaction times 4 ~ 12h at temperature of reaction 120 ~ 200 DEG C, reaction generates ferric oxide and hydrochloric acid soln; Ferric oxide makes pigment or coating, and HCl recovery recycles.
2. a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate according to claim 1, is characterized in that: in described step (1), flyash and mass concentration are the batching mass ratio of the hydrochloric acid of 26 ~ 30% is 1:(1.05 ~ 1.10).
3. a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate according to claim 1, is characterized in that: in described step (1), temperature of reaction is 100 ~ 110 DEG C.
4. a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate according to claim 1, is characterized in that: in described step (1), the reaction times is 1 ~ 2h.
5. a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate according to claim 1, is characterized in that: the concentration of the dilute hydrochloric acid in described step (2) is 0.1%.
6. a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate according to claim 1, is characterized in that: the reductive agent in described step (3) is iron filings.
7. a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate according to claim 1, is characterized in that: in described step (4), the add-on of iron protochloride is 5 ~ 20% of the aluminum chloride molar weight contained in solution.
8. a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate according to claim 1, is characterized in that: in described step (5), the add-on of water is 5 ~ 40% of water content in step (4) filtrate.
9. a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate according to claim 1, is characterized in that: in described step (6), temperature of reaction is 150 ~ 180 DEG C.
10. a kind of method taking flyash as raw material iron protochloride induced crystallization and prepare Aluminum Chloride Hexahydrate according to claim 1, is characterized in that: in described step (6), the reaction times is 6 ~ 10h.
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| CN104961757A (en) * | 2015-05-28 | 2015-10-07 | 北京交通大学 | Method for preparing metal organic framework material by using fly ash |
| CN105540632A (en) * | 2015-12-21 | 2016-05-04 | 华东理工常熟研究院有限公司 | Method for purifying crystalline aluminum chloride |
| CN106044997B (en) * | 2016-07-08 | 2019-08-06 | 哈尔滨工业大学深圳研究生院 | One kind containing Fe3+The processing method of heavy metal wastewater thereby |
| CN106044999B (en) * | 2016-07-08 | 2019-08-06 | 哈尔滨工业大学深圳研究生院 | A kind of method of Fenton group technology processing waste water |
| CN110577266B (en) * | 2019-09-29 | 2022-05-03 | 李子璇 | Purification method of waste mixed acid liquor |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1430449A (en) * | 1922-03-06 | 1922-09-26 | Grasselli Chemical Co | Method of preparing aluminum-chloride crystals |
| US1875105A (en) * | 1926-08-07 | 1932-08-30 | Niagara Smelting Corp | Method of and apparatus for mineral chlorination |
| US3406010A (en) * | 1965-09-08 | 1968-10-15 | Anaconda Co | Recovery of pure crystals of aici3.6h2o and production of aluminum oxide product therefrom |
| US4331637A (en) * | 1981-04-20 | 1982-05-25 | Reynolds Metals Company | Process for purifying aluminum chloride |
| NO300004B1 (en) * | 1994-03-30 | 1997-03-17 | Elkem Materials | Process for the recovery of metal chloride from silicon or ferrosilicon alloy reacted with chlorinating agents |
| CN101234774B (en) * | 2008-03-04 | 2010-04-21 | 华东理工大学 | Method for preparing aluminum oxide from coal series kaolinite rock or coal gangue |
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