CN103159263B - Treatment method of artificial rutile mother solution - Google Patents
Treatment method of artificial rutile mother solution Download PDFInfo
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- CN103159263B CN103159263B CN201310111493.1A CN201310111493A CN103159263B CN 103159263 B CN103159263 B CN 103159263B CN 201310111493 A CN201310111493 A CN 201310111493A CN 103159263 B CN103159263 B CN 103159263B
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- iron
- artificial rutile
- concentration
- iron trichloride
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Abstract
The invention discloses a treatment method of an artificial rutile mother solution, which comprises the following steps: preconcentrating an artificial rutile mother solution by heating to enhance the Fe<3+> concentration in the mother solution to 150 g/L above, mixing with an iron source, reacting in a fluidized bed reactor into which HCl gas is introduced to enhance the iron concentration in the mother solution, filtering the acidolysis solution, crystallizing by freezing to obtain the iron chloride crystal, and finally, roasting the crystal to obtain high-grade iron red. The method disclosed by the invention has the advantages of simple technical process, low energy consumption, fewer byproducts, energy saving and environmental protection, is easy to operate, implements cyclic utilization of chlorine element in the mother solution, and recycles all the substances in the mother solution. Besides, the method purifies and separates the iron chloride in the mother solution, and the iron chloride can be roasted to obtain the high-grade iron red to satisfy the market demands.
Description
Technical field
The treatment process that the present invention relates to a kind of artificial rutile mether liquor, belongs to chemical field.
Background technology
Utilize hydrochloric acid leaching ilmenite concentrate, can effectively remove the impurity such as iron and most of CaO, MgO, Al2O3, MnO in ilmenite concentrate, obtain containing TiO
2content is 88%～96% high-grade artificial rutile.Hydrochloric acid leaching legal system has for the production technique of artificial rutile that leaching velocity is fast, removal of impurities ability strong, product grade advantages of higher, is therefore particularly suitable for processing various types of ilmenite concentrates.But, manufacture in artificial rutile process at use hydrochloric acid leaching ilmenite concentrate, the dissolving such as iron compound and calcium and magnesium oxides in ilmenite concentrate forms chlorate and enters meeting formation artificial rutile mether liquor in solution, owing to containing various metals muriate and iron(ic) chloride in artificial rutile mether liquor, add the unreacted hydrochloric acid of part in addition, make its very difficult recycling.
Shown in the classical group of artificial rutile mether liquor becomes to see the following form:
In being the application for a patent for invention specification sheets of CN 1657426A, publication number discloses a kind of method for recovery and treatment components from mother liquid of artificial rutile.The method is by after concentrated artificial rutile mether liquor heating, ferric chloride concn is wherein improved, then spray into roasting kiln roasting, iron(ic) chloride generation pyrolysis under high temperature oxidation atmosphere, form hydrogen chloride gas and the soild oxide taking ferric oxide as master, hydrogen chloride gas water absorption obtains the hydrochloric acid of regenerating.Although the method has realized the recycle of chlorion, energy consumption is very high, and the mother liquor that one ton of artificial rutile of every processing produces needs the heat of about 6,400,000 kilocalories, and needing Sweet natural gas is 800Nm
3left and right, and the heat of this processing mode 70% all consumes on evaporation of water latent heat, advocates for a long time under energy-conservation policies and regulations in country always, this method does not obviously have sustainability; What is more important, the method, due to not to the separation of purifying of the iron(ic) chloride in mother liquor, makes its product of roasting Fe
2o
3in contain the more impurity such as MgO and CaO, Fe
2o
3purity only can arrive 90% left and right, causes its purposes little, can only serve as the raw material of steel-making.
The patent No. is that the patent of invention of ZL 90105886.6 discloses a kind of method of obtaining through refining ultrafine iron oxide from dilute hydrochloric acid rutile mether liquor.The method is to be the swarf of 2～25 millimeters by adding particle diameter in rutile mether liquor, at 30～100 DEG C of temperature, process to PH and be about at 3.8 o'clock, add again polyacrylamide precipitation, after the logical chlorine oxidation of clear liquid, by the solution of chloride containing iron semi continuous under 25～70 DEG C of temperature strong mixings add ammoniacal liquor to PH be 5～8 o'clock, generate amorphous ferric hydroxide colloidal precipitation, by this precipitation slurry that to make containing Fe be 0.5～15%, add successively iron filings, trivalent iron salt, tensio-active agent and positively charged mass treatment, filter, filter cake drying is ground and is made ultrafine iron oxide Huang, gained iron oxide yellow is calcined in calcining furnace and can be obtained brown iron oxide.Although the method can obtain iron oxide yellow or the iron oxide red of high-quality, but technical process complexity, and in process, also will use poisonous chlorine, and in artificial rutile mether liquor, chlorine element fails to be recycled utilization, the waste liquid of a large amount of chloride ion-containings of by-product brings severe contamination to environment.
The patent No. is that the patent of invention of ZL 89105794.3 discloses a kind of process for continuous production of high-purity iron oxide from ferrous salt, the method is taking the waste material (or waste liquid) containing ferrous salt as raw material, after purifying treatment, join together with the crystal seed of preparing in the mechanical stirring aeration tank of one group of series connection, adding ammonia to adjust pH value is between 2.5～6, and maintain 75～90 DEG C of solution temperatures, make ferrous ion oxidation neutralization form crystalloid α-Fe
2o
3product, the isolated ammonium solution that contains reacts with lime or magnesia in ammonia still process groove, during recovery ammonia returns, recycles with oxidation trough.Although the method has obtained ferric oxide, ammonia is also regenerated, and technical process is very complicated, and chlorine element is not still recycled utilization, and the waste liquid of a large amount of chloride containing calcium of by-product, magnesium chloride, brings pollution to environment.
Similarly patent also has a lot, but almost prior art all just reclaims iron to artificial rutile mether liquor and does not consider the recycling of chlorine element, the chlorate of a large amount of calcics of by-product, magnesium brings pollution to environment, and too high by the regenerate method energy consumption of hydrochloric acid of spray roasting, and the ferric oxide grade obtaining is very low.
Summary of the invention
Object of the present invention is just for above-mentioned the deficiencies in the prior art, a kind for the treatment of process of artificial rutile mether liquor is provided, the inventive method technical process is simple, easy to operate, uses the method to process mother liquor energy consumption low, realize the recycle and reuse of chlorine element in mother liquor, all substances in mother liquor are recycled, and by product is few, energy-conserving and environment-protective, and the inventive method has been carried out purifying to the iron(ic) chloride in mother liquor and has been separated, and can roasting make high-grade iron oxide red for answering the market requirement.
To achieve these goals, the technical solution used in the present invention is such:
A treatment process for artificial rutile mether liquor, comprises the following steps:
(1) heating artificial rutile mether liquor to 85～110 DEG C, pre-concentration mother liquor makes Fe in mother liquor
3+more than concentration is brought up to 150g/L;
(2) in the mother liquor after pre-concentration, add source of iron to mix and form solid-liquid mixed slurry;
(3) solid-liquid mixed slurry is added to fluidized-bed reactor, pass into HCl gas in fluidized-bed reactor, in maintenance slurry, acid concentration is constant in 200～220g/L, and acidolysis reaction occurs for the source of iron in slurry and HCl, forms acid hydrolysis solution;
(4) as Fe in acid hydrolysis solution
3+concentration reaches 800 g/L when above, filters acid hydrolysis solution;
(5) acid hydrolysis solution after frozen cooling filtration, makes iron trichloride crystallization wherein, and filtering separation obtains iron trichloride crystal, and clear liquid returns to fluidized-bed reactor in step (3) and participates in acidolysis reaction; Frozen cooling is to make acid hydrolysis solution be cooled to 0-10 DEG C with the salt solution of-5 DEG C, makes iron trichloride crystallization wherein.
(6) to make its water content be 12～15% to dry iron trichloride crystal, and the dried iron trichloride crystal of roasting pyrolysis obtains higher-grade iron oxide red, and wherein the tail gas of pyrolysis iron trichloride is for dry iron trichloride crystal.
Wherein, step (1) utilization is prepared the waste-heat pre-concentration mother liquor of artificial rutile ilmenite concentrate oxidized tail gas, has both solved the exhaust emissions problem of preparing in artificial rutile process, has also saved the energy.
In step (2), source of iron used is one or more in sulfate slag, iron-containing tailing and iron ore concentrate.
Sulfate slag is a kind of powdery tailings producing in waste sulfuric acid process taking sulfurous iron ore; Iron-containing tailing is the waste after ore dressing; Iron ore concentrate is the higher discarded ore deposit of iron-holder after ilmenite concentrate hydrochloric acid leaching.Because sulfate slag, iron-containing tailing, iron ore concentrate are all the discarded ore deposits that iron-holder is higher, with they increase the concentration of iron in mother liquor, solved the utilization of waste material problem of these mineral, there is good environmental benefit.
The HCl gas passing in step (3) is the tail gas of pyrolysis iron trichloride in step (6), has realized two recycles of chlorine element and the energy, save energy.
The insolubles that filtration acid hydrolysis solution obtains is: Si0
2, the raw material of cement is prepared in cement mill just, and the insolubles that step (4) filtration acid hydrolysis solution is obtained is delivered to cement mill and is processed, and makes all substances in mother liquor all obtain utilization, has realized zero waste discharge of mother liquid disposal, has good environmental benefit.
The iron oxide red grade obtaining in order to improve roasting also comprises re-crystallization step after described step (5), puts into 20% hydrochloric acid carry out recrystallization by freezing and crystallizing in the iron trichloride crystal obtaining, and the purity of iron trichloride is reached more than 99%.
As the Ca of clear liquid described in step (5)
2+, Mg
2+when any material exceedes the concentration of 120g/L, clear liquid no longer returns to fluidized-bed reactor in step (3) and participates in acidolysis reaction, in order to avoid reduce the Fe of artificial rutile mether liquor
3+concentration.With the clear liquid that does not participate in acidolysis reaction in carbide slag neutralization procedure (5), the throw out that neutralization obtains is Ca (OH)
2, Mg (OH)
2, Fe
2 (oH)
3, filtering separation is delivered to cement mill as raw material, and remaining solution is calcium chloride solution, is carried out mist projection granulating and can make Calcium Chloride Powder Anhydrous, has realized all substances in mother liquor and has been utilized.
Compared with prior art, the invention has the advantages that:
The present invention improves Fe in mother liquor with hydrochloric acid reaction after artificial rutile mether liquor is added to the iron content such as sulfate slag or iron ore abandoned mine in fluidized-bed reactor
3+concentration, then filter and obtain iron trichloride by freezing and crystallizing, iron(ic) chloride in mother liquor is carried out purifying and separated, iron trichloride after recrystallization improves its purity again pyrolysis be high-quality brown iron oxide, pyrolysis tail gas can be back to hydrolysis procedure recycle, and utilizes its using waste heat from tail gas that crystallization iron trichloride is dehydrated before pyrolysis.The inventive method technical process is simple, easy to operate, use the method to process mother liquor energy consumption low, realize the recycle and reuse of chlorine element in mother liquor, all substances in mother liquor are recycled, and by product is few, energy-conserving and environment-protective, and the inventive method has been carried out purifying to the iron(ic) chloride in mother liquor and has been separated, and can roasting make high-grade iron oxide red for answering the market requirement.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the inventive method.
Embodiment
In order more clearly to understand object of the present invention, technical scheme and beneficial effect, below the present invention is described further, but protection scope of the present invention is not limited in following examples.
In following examples, artificial rutile mether liquor used is composed as follows:
Free hydrochloric acid 116.7g/L, Fe
3+97.2g/L, Fe
2+4.2g/L, AL
3+4.2g/L, Al
3+0.22g/L, Ca
2+0.41g/L, Mg
2+3.16g/L, Si
4+0.03g/L, Ti
4+0.04g/L, Mn
2+0.63g/L, V
5+0.05g/L.
Embodiment 1:
(1) with ilmenite concentrate oxidizing tower tail gas heating pre-concentration artificial rutile mether liquor out, mother liquor is warming up to 85～110 DEG C, the Fe in mother liquor
3+more than concentration is brought up to 150g/L.
(2) mother liquor after pre-concentration and sulfate slag are uniformly mixed to form solid-liquid mixed slurry;
(3) solid-liquid mixed slurry is added in fluidized-bed reactor, the logical hydrogen chloride gas of fluidized-bed reactor and compressed-air actuated mixed gas, wherein hydrogen chloride gas is the hydrogen chloride tail gas that step (6) iron trichloride pyrolysis produces, in maintenance slurry, acid concentration is constant in 200～220g/L, there is acidolysis reaction in the source of iron in slurry and HCl, forms acid hydrolysis solution;
(4) as Fe in acid hydrolysis solution
3+concentration reaches 800 g/L when above, acid hydrolysis solution is emitted, and remain at 80 DEG C of above temperature and filter, and sour insoluble solid impurities goes to cement mill as raw material;
(5) acid hydrolysis solution after filtration cools to 0～10 DEG C with-5 DEG C of salt solution, frozen cooling crystallization iron trichloride crystal, and filtering separation, clear liquid returns to fluidized-bed reactor in step (3) and participates in acidolysis reaction.As Ca in the reuse stillness of night repeatedly
2+, Mg
2+when any material exceedes the concentration of 120g/L, not recycling of clear liquid, neutralizes it with carbide slag, and neutralization precipitation thing filters to isolate the cement mill of making a return journey as raw material, and calcium chloride solution carries out mist projection granulating and produces Calcium Chloride Powder Anhydrous.
(6) crystallization iron trichloride is carried out to recrystallization 1 time with 20% hydrochloric acid, the purity of iron trichloride is 99.2%, and what in its process, produce delivers to hydrolysis procedure recycling containing acid waste liquid.
(7) massfraction that obtains water through the iron trichloride of recrystallization through drying and dehydrating only has 12～15% solid particulate, then enter roasting in fluidized-bed and issue heat-dissipating decomposition reaction 525 DEG C of temperature, the solid oxidation iron powder that finally obtains hydrogen chloride gas and high-quality, its chemical composition sees the following form shown in 1.The tail gas that pyrolysis produces first utilizes the iron trichloride of its waste heat counterweight crystallization to carry out after drying and dehydrating, is back to hydrolysis procedure and is dissolved as hydrochloric acid in utilization.
Embodiment 2:
Operation is with embodiment 1, difference is: the iron oxide source that enters acidolysis groove is that all iron content is 68% iron ore concentrate but not sulfate slag, after 1 recrystallization, the purity of iron trichloride is 99.4%, and pyrolysis temperature is 590 DEG C, and its chemical composition of the brown iron oxide obtaining sees the following form shown in 1.
Embodiment 3:
Operation is with embodiment 1, difference is: the iron oxide source that enters acidolysis groove is that all iron content is 68% iron ore concentrate but not sulfate slag, after 2 recrystallizations, the purity of iron trichloride is 99.8%, and pyrolysis temperature is 685 DEG C, and its chemical composition of the brown iron oxide obtaining sees the following form shown in 1.
Claims (8)
1. a treatment process for artificial rutile mether liquor, is characterized in that: comprise the following steps:
(1) heating artificial rutile mether liquor to 85～110 DEG C, pre-concentration mother liquor makes Fe in mother liquor
3+more than concentration is brought up to 150g/L;
(2) in the mother liquor after pre-concentration, add source of iron to mix and form solid-liquid mixed slurry;
(3) solid-liquid mixed slurry is added to fluidized-bed reactor, pass into HCl gas in fluidized-bed reactor, in maintenance slurry, acid concentration is constant in 200～220g/L, and acidolysis reaction occurs for the source of iron in slurry and HCl, forms acid hydrolysis solution;
(4) as Fe in acid hydrolysis solution
3+concentration reaches 800 g/L when above, filters acid hydrolysis solution;
(5) acid hydrolysis solution after frozen cooling filtration, makes iron trichloride crystallization wherein, and filtering separation obtains iron trichloride crystal, and clear liquid returns to fluidized-bed reactor in step (3) and participates in acidolysis reaction; (6) re-crystallization step: put into 20% hydrochloric acid in the iron trichloride crystal that freezing and crystallizing is obtained and carry out recrystallization, the purity of iron trichloride is reached more than 99%;
(7) to make its water content be 12～15% to dry iron trichloride crystal, and the dried iron trichloride crystal of roasting pyrolysis obtains higher-grade iron oxide red, and wherein the tail gas of pyrolysis iron trichloride is for dry iron trichloride crystal.
2. the treatment process of a kind of artificial rutile mether liquor according to claim 1, is characterized in that: in described step (1), utilize the waste-heat pre-concentration mother liquor of preparing artificial rutile ilmenite concentrate oxidized tail gas.
3. the treatment process of a kind of artificial rutile mether liquor according to claim 1, is characterized in that: the source of iron in described step (2) is one or more in sulfate slag, iron-containing tailing and iron ore concentrate.
4. the treatment process of a kind of artificial rutile mether liquor according to claim 1, is characterized in that: the HCl gas passing in described step (3) is the tail gas of pyrolysis iron trichloride in step (6).
5. the treatment process of a kind of artificial rutile mether liquor according to claim 1, is characterized in that: the insolubles that described step (4) filtration acid hydrolysis solution obtains is delivered to cement mill and processed.
6. the treatment process of a kind of artificial rutile mether liquor according to claim 1, is characterized in that: the salt solution with-5 DEG C in described step (5) makes acid hydrolysis solution be cooled to 0-10 DEG C, makes iron trichloride crystallization wherein.
7. the treatment process of a kind of artificial rutile mether liquor according to claim 1, is characterized in that: as the Ca of clear liquid described in step (5)
2+, Mg
2+when any material exceedes the concentration of 120g/L, clear liquid no longer returns to fluidized-bed reactor in step (3) and participates in acidolysis reaction.
8. the treatment process of a kind of artificial rutile mether liquor according to claim 7, is characterized in that: with the clear liquid that does not participate in acidolysis reaction in carbide slag neutralization procedure (5).
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| CN201310111493.1A CN103159263B (en) | 2013-04-02 | 2013-04-02 | Treatment method of artificial rutile mother solution |
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| CN103159263B true CN103159263B (en) | 2014-09-10 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528834B (en) * | 2014-12-15 | 2016-02-03 | 宜宾天原集团股份有限公司 | Artificial rutile mether liquor recycling novel method |
| CN105110784B (en) * | 2015-08-03 | 2017-04-12 | 宜宾天原集团股份有限公司 | Method for preparing manganese zinc ferrite by using artificial rutile mother liquor |
| TWI637913B (en) * | 2017-12-08 | 2018-10-11 | 葉俊良 | Curing manufacturing method of hexahydrate ferric chloride and curing manufacturing system thereof |
| CN111593210A (en) * | 2020-05-26 | 2020-08-28 | 宜宾天原海丰和泰有限公司 | Method for treating artificial rutile mother liquor |
| CN112723311A (en) * | 2020-12-28 | 2021-04-30 | 宜宾天原海丰和泰有限公司 | Method for comprehensively utilizing artificial rutile mother liquor by utilizing iron ore |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132182A (en) * | 1994-12-27 | 1996-10-02 | 拜尔公司 | Process for thermal treatment of iron oxides in circulating fluidised bed |
| CN1657426A (en) * | 2005-02-17 | 2005-08-24 | 攀钢集团攀枝花钢铁研究院 | Method for recovery and treatment components from mother liquid of artificial rutile |
| CN1752030A (en) * | 2005-08-10 | 2006-03-29 | 攀钢集团攀枝花钢铁研究院 | Method of removig calcium, magnesium and aluminium in artificial rutile mother liquor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59115744A (en) * | 1982-12-21 | 1984-07-04 | Osaka Gas Co Ltd | Wet type oxidation processing catalyst |
-
2013
- 2013-04-02 CN CN201310111493.1A patent/CN103159263B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132182A (en) * | 1994-12-27 | 1996-10-02 | 拜尔公司 | Process for thermal treatment of iron oxides in circulating fluidised bed |
| CN1657426A (en) * | 2005-02-17 | 2005-08-24 | 攀钢集团攀枝花钢铁研究院 | Method for recovery and treatment components from mother liquid of artificial rutile |
| CN1752030A (en) * | 2005-08-10 | 2006-03-29 | 攀钢集团攀枝花钢铁研究院 | Method of removig calcium, magnesium and aluminium in artificial rutile mother liquor |
Non-Patent Citations (1)
| Title |
|---|
| JP昭59-115744A 1984.07.04 |
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