Method for combined treatment of high-calcium-magnesium artificial rutile mother liquor by titanium steel

Abstract

The invention discloses a method for combined treatment of high-calcium-magnesium artificial rutile mother liquor by using titanium and steel, which comprises the following steps: placing the artificial rutile mother liquor in a waste acid roasting device of a cold rolling pickling line for high-temperature oxidizing roasting treatment to obtain a diluted hydrochloric acid primary product and a ferric oxide by-product containing calcium and magnesium impurities; and the ferric oxide by-product containing the calcium and magnesium impurities and vanadium-titanium-iron concentrate are produced according to the proportion, and the oxidized pellets for blast furnace ironmaking are obtained. According to the method, the high-calcium-magnesium artificial rutile mother liquor is organically fused and butted with a waste acid roasting device of a cold rolling pickling line of an iron and steel plant for roasting treatment, so that cyclic utilization of by-products such as diluted hydrochloric acid and Fe2O3 generated by the high-calcium-magnesium artificial rutile mother liquor can be efficiently realized; the problems of high-calcium-magnesium artificial rutile mother liquor treatment, environmental protection and high treatment cost can be effectively solved, and the blast furnace burden structure is optimized to a certain extent.

Description

Technical Field

[0001] The present invention relates to the technical field of recycling of high-calcium and magnesium artificial rutile mother liquor, and particularly to a method for jointly treating high-calcium and magnesium artificial rutile mother liquor by titanium and steel. Background Art

[0002] Due to the natural properties of certain vanadium-titanium magnetite ores, a large amount of hydrochloric acid waste liquor, namely high-calcium and magnesium mother liquor of artificial rutile, will be generated during the production of artificial rutile by the hydrochloric acid method from titanium concentrate. This mother liquor contains hydrochloric acid with a certain concentration and high concentrations of iron ions, calcium ions, magnesium ions, etc. If directly discharged, it will cause environmental pollution, and useful components such as iron ions will also be wasted. To solve these problems and achieve the comprehensive utilization of resources and environmental governance and protection, the joint treatment of high-calcium and magnesium artificial rutile mother liquor by titanium and steel is of great significance for the research on the efficient recycling of the mother liquor.

[0003] Based on this, the existing technology still needs to be improved. Summary of the Invention

[0004] To solve the above technical problems, an embodiment of the present invention provides a method for jointly treating high-calcium and magnesium artificial rutile mother liquor by titanium and steel to solve the problem of the reuse of the artificial rutile mother liquor in the existing technology.

[0005] To solve the above technical problems, some embodiments of the present invention disclose a method for jointly treating high-calcium and magnesium artificial rutile mother liquor. The artificial rutile mother liquor is subjected to high-temperature oxidation roasting treatment in a waste acid roasting device of a cold rolling pickling line to obtain a primary product of dilute hydrochloric acid and a by-product of ferric oxide containing calcium and magnesium impurities; the by-product of ferric oxide containing calcium and magnesium impurities is proportionally mixed with vanadium-titanium iron concentrate to produce oxidized pellets. In some embodiments, during the high-temperature oxidation roasting treatment, the furnace temperature is 680-690 °C, the spraying flow rate is 2.80-2.90 m 3 / h, the air-coal ratio is 1.30-1.38, and the absorption tower flow rate is 3.70-3.80 m 3 / h.

[0006] In some embodiments, after the primary product of dilute hydrochloric acid is concentrated and absorbed, a regenerated new hydrochloric acid with a concentration greater than 19% is obtained.

[0007] In some embodiments, when the by-product of ferric oxide containing calcium and magnesium impurities is proportionally mixed with vanadium-titanium iron concentrate to produce oxidized pellets, the roasting parameters include: a preheating temperature of 780 °C - 820 °C, a preheating time of 8-12 min, a roasting temperature of 1250-1280 °C, and a roasting time of 13-17 min.

[0008] In some embodiments, the obtained oxidized pellets have a compressive strength of 2481~3708 / N·piece.

[0009] In some embodiments, in the obtained oxidized pellets, the mass percentage of TFe is greater than 65.50%.

[0010] In some embodiments, before the high-temperature oxidation roasting treatment of the artificial rutile mother liquor, filtration and pre-concentration treatments are first performed.

[0011] In some embodiments, after the high-temperature oxidation roasting treatment, through a double cyclone dust collector, a pre-concentrator, an absorption tower, and a washing tower in sequence, a regenerated new hydrochloric acid with a concentration greater than 19% is obtained.

[0012] In some embodiments, the oxidized pellets are used as blast furnace burden.

[0013] In some embodiments, the regenerated new hydrochloric acid is used for leaching titanium concentrate to prepare artificial rutile or returned to the steel plate pickling line to pickle steel plates.

[0014] Adopting the above technical solutions, the present invention has at least the following beneficial effects: A method for jointly treating high-calcium and high-magnesium artificial rutile mother liquor by titanium and steel provided by the present invention organically combines artificial rutile with the cold rolling pickling line of a steel plant, not only solves the problem of reprocessing of artificial rutile mother liquor, but also can efficiently realize the recovery of waste acid and the recycling of elements such as iron, effectively solves the problems of treatment and environmental protection of high-calcium and high-magnesium artificial rutile mother liquor and the high treatment cost, and also optimizes the blast furnace burden structure to a certain extent, truly realizing the organic integration of the titanium and steel industries. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for description in the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0016] Figure 1 It is a flow chart of a method for jointly treating high-calcium and high-magnesium artificial rutile mother liquor by titanium and steel disclosed in some embodiments of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0017] The following will further describe in detail the embodiments of the present disclosure in conjunction with the drawings. The detailed description and drawings of the following embodiments are used to exemplarily illustrate the principles of the present disclosure, but cannot be used to limit the scope of the present disclosure. The present disclosure can be implemented in many different forms, not limited to the specific embodiments disclosed herein, but including all technical solutions falling within the scope of the claims.

[0018] The present disclosure provides these embodiments to make the present disclosure thorough and complete, and to fully convey the scope of the present disclosure to those skilled in the art. It should be noted that: unless otherwise specifically stated, the relative arrangements of components and steps set forth in these embodiments, the components of materials, numerical expressions and values should be construed as merely exemplary, rather than as limitations.

[0019] It should be noted that in the description of the present disclosure, unless otherwise specified, the meaning of "a plurality" is greater than or equal to two; the orientation or positional relationship indicated by terms such as "upper", "lower", "left", "right", "inner", "outer", etc. is only for the convenience of describing the present disclosure and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus cannot be construed as a limitation of the present disclosure. When the absolute position of the object being described changes, the relative positional relationship may also change accordingly.

[0020] In addition, the "first", "second" and similar terms used in the present disclosure do not denote any order, quantity or importance, but are only used to distinguish different parts. "Vertical" is not strictly vertical, but within the allowable error range. "Parallel" is not strictly parallel, but within the allowable error range. Words such as "comprising" or "including" mean that the elements before the word cover the elements listed after the word, and do not exclude the possibility of also covering other elements.

[0021] It should also be noted that in the description of the present disclosure, unless otherwise clearly specified and limited, the terms "mounted", "connected" and "coupled" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be directly connected, or indirectly connected through an intermediate medium. For those of ordinary skill in the art, the specific meanings of the above terms in the present disclosure can be understood according to specific circumstances. When it is described that a specific device is located between a first device and a second device, there may or may not be an intermediate device between the specific device and the first device or the second device.

[0022] All terms used in the present disclosure have the same meaning as understood by those of ordinary skill in the art to which the present disclosure pertains, unless otherwise specifically defined. It should also be understood that terms defined in a general dictionary, such as those, should be interpreted as having a meaning consistent with their meaning in the context of the relevant art, and should not be interpreted in an idealized or overly formal sense, unless specifically defined as such here.

[0023] Technologies, methods and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the technologies, methods and devices should be regarded as part of the specification.

[0024] As Figure 1 shown, some embodiments of the present invention disclose a method for jointly treating high-calcium and high-magnesium artificial rutile mother liquor with titanium steel. The artificial rutile mother liquor is placed in a waste acid roasting device of a cold rolling pickling line for high-temperature oxidation roasting treatment to obtain a preliminary product of dilute hydrochloric acid and a by-product of iron oxide containing calcium and magnesium impurities. The by-product of iron oxide containing calcium and magnesium impurities is proportionally mixed with vanadium-titanium iron concentrate for production to obtain oxidized pellets. The obtained oxidized pellets can be used as blast furnace burden, optimizing the blast furnace burden structure to a certain extent. To save energy, before the high-temperature oxidation roasting treatment of the artificial rutile mother liquor, filtration and pre-concentration treatment are first required. On the one hand, impurities in the mother liquor are filtered out to prevent clogging of the roasting nozzle and affecting the atomization effect. On the other hand, the mother liquor is concentrated to be similar to the total acid value of ΣHCl in the pickling solution, ensuring that the regenerated new acid can not only meet the leaching of titanium concentrate by the hydrochloric acid method but also meet the pickling requirements of steel plates, realizing the organic integration of the hydrochloric acid method artificial rutile production line and the cold plate steel pickling production line, achieving resource and equipment sharing, greatly reducing equipment investment, and enhancing the overall competitiveness of the industry, which is a first in China and abroad.

[0025] Among them, during the high-temperature oxidation roasting treatment, the furnace temperature can be set at 680 - 690 °C, the spraying flow rate can be set at 2.80 - 2.90 m 3 / h, the air-coal ratio can be set at 1.30 - 1.38, and the absorption tower flow rate can be set at 3.70 - 3.80 m 3 / h, which can achieve better roasting effects. After the preliminary product of dilute hydrochloric acid is concentrated and absorbed, regenerated new hydrochloric acid with a concentration greater than 19% is obtained, that is, after the high-temperature oxidation roasting treatment, it successively passes through a double cyclone dust collector, a pre-concentrator, an absorption tower, and a washing tower to obtain regenerated new hydrochloric acid with a concentration greater than 19%. This regenerated new hydrochloric acid can be used for leaching titanium concentrate to prepare artificial rutile and can also be returned to the steel plate pickling line to pickle steel plates, realizing the reuse of hydrochloric acid in the artificial rutile mother liquor.

[0026] In some embodiments of the present invention, when the by-product of iron oxide containing calcium and magnesium impurities is proportionally mixed with vanadium-titanium iron concentrate for production to obtain oxidized pellets, in order to obtain ideal pellets, the roasting parameters can be set as follows: preheating temperature 780 °C - 820 °C, preheating time 8 - 12 min, roasting temperature 1250 - 1280 °C, and roasting time 13 - 17 min. The obtained oxidized pellets have a compressive strength of 2481 - 3708 / N·piece, and in terms of mass percentage, TFe is greater than 65.50%.

[0027] Example 1 A method for jointly treating high-calcium and high-magnesium artificial rutile mother liquor with titanium steel, comprising the following steps: Step 1: After filtration and concentration, the high-calcium-magnesium artificial rutile mother liquor enters the roasting furnace for roasting and recovery treatment. During the roasting treatment, the furnace temperature is set at 680 °C, the spraying flow rate is set at 2.80 m 3 / h, the air-coal ratio is set at 1.30, and the absorption tower flow rate is set at 3.80 m 3 / h. After roasting, iron(III) oxide by-products containing calcium and magnesium impurities and crude hydrochloric acid products are obtained. The crude hydrochloric acid product coming out of the roasting furnace is successively passed through a double cyclone dust collector, a pre-concentrator, an absorption tower and a washing tower to obtain regenerated new hydrochloric acid with a mass concentration of 19.78%, and the HCl recovery rate is 99.50%; Step 2: The Fe2O3 by-product containing calcium and magnesium impurities obtained by roasting treatment in Step 1 is proportioned with vanadium-titanium iron concentrate at a ratio of 40% by mass to produce oxidized pellets. The roasting parameters are as follows: preheating temperature 800 °C, preheating time 10 min, roasting temperature 1250 °C, and roasting time 15 min. The compressive strength of the obtained oxidized pellets is 3708 / N·piece, and the mass content of TFe is 65.75%, which can be used as high-quality raw materials for blast furnace ironmaking.

[0028] Example 2 A method for jointly treating high-calcium-magnesium artificial rutile mother liquor by titanium and steel, comprising the following steps: Step 1: After filtration and concentration, the high-calcium-magnesium artificial rutile mother liquor enters the roasting furnace for roasting and recovery treatment. During the roasting treatment, the furnace temperature is set at 690 °C, the spraying flow rate is set at 2.90 m 3 / h, the air-coal ratio is set at 1.38, and the absorption tower flow rate is set at 3.70 m 3 / h. After roasting, iron(III) oxide by-products containing calcium and magnesium impurities and crude hydrochloric acid products are obtained. The crude hydrochloric acid product coming out of the roasting furnace is successively passed through a double cyclone dust collector, a pre-concentrator, an absorption tower and a washing tower to obtain regenerated new hydrochloric acid with a mass concentration of 20.44%, and the HCl recovery rate is 99.60%; Step 2: The Fe2O3 by-product containing calcium and magnesium impurities obtained by roasting treatment in Step 1 is proportioned with vanadium-titanium iron concentrate at a ratio of 60% by mass to produce oxidized pellets. The roasting parameters are as follows: preheating temperature 800 °C, preheating time 12 min, roasting temperature 1280 °C, and roasting time 17 min. The compressive strength of the obtained oxidized pellets is 2736 / N·piece, and the mass content of TFe is 66.50%, which can be used as high-quality raw materials for blast furnace ironmaking.

[0029] Example 3 A method for jointly treating high-calcium-magnesium artificial rutile mother liquor by titanium and steel, comprising the following steps: Step 1: After the high-calcium and high-magnesium synthetic rutile mother liquor is filtered and concentrated, it enters a roasting furnace for roasting and recovery treatment. During the roasting treatment, the furnace temperature is set at 685 °C, the spraying flow rate is set at 2.85 m 3 / h, the air-coal ratio is set at 1.34, and the absorption tower flow rate is set at 3.75 m 3 / h. After roasting is completed, a by-product of ferric oxide containing calcium and magnesium impurities and a preliminary hydrochloric acid product are obtained. The preliminary hydrochloric acid product coming out of the roasting furnace is successively passed through a double cyclone dust collector, a pre-concentrator, an absorption tower, and a washing tower to obtain a regenerated new hydrochloric acid with a mass concentration of 20.15%, and the HCl recovery rate is 99.58%; Step 2: The Fe2O3 by-product containing calcium and magnesium impurities obtained by roasting treatment in Step 1 is proportioned with vanadium-titanium iron concentrate at a ratio of 80% by mass to produce oxidized pellets. The roasting parameters are as follows: preheating temperature 820 °C, preheating time 8 min, roasting temperature 1250 °C, and roasting time 13 min. The compressive strength of the obtained oxidized pellets is 2481 / N·piece, and the mass content of TFe is 67.20%, which can be used as high-quality raw materials for blast furnace ironmaking.

[0030] Comparative Example 1 A method for jointly treating high-calcium and high-magnesium synthetic rutile mother liquor by titanium and steel, comprising the following steps: Step 1: After the high-calcium and high-magnesium synthetic rutile mother liquor is filtered and concentrated, it enters a roasting furnace for roasting and recovery treatment. During the roasting treatment, the furnace temperature is set at 670 °C, the spraying flow rate is set at 2.80 m 3 / h, the air-coal ratio is set at 1.30, and the absorption tower flow rate is set at 3.80 m 3 / h. After roasting is completed, a by-product of ferric oxide containing calcium and magnesium impurities and a preliminary hydrochloric acid product are obtained. The preliminary hydrochloric acid product coming out of the roasting furnace is successively passed through a double cyclone dust collector, a pre-concentrator, an absorption tower, and a washing tower to obtain a regenerated new hydrochloric acid with a mass concentration of 18.73%, and the HCl recovery rate is 98.85%; Step 2: The Fe2O3 by-product containing calcium and magnesium impurities obtained by roasting treatment in Step 1 is proportioned with vanadium-titanium iron concentrate at a ratio of 30% by mass to produce oxidized pellets. The roasting parameters are as follows: preheating temperature 760 °C, preheating time 7 min, roasting temperature 1200 °C, and roasting time 12 min. The compressive strength of the obtained oxidized pellets is 1812 / N·piece, and the mass content of TFe is 65.24%. The compressive strength is relatively low, affecting the blast furnace smelting effect.

[0031] Comparative Example 2 A method for jointly treating high-calcium and high-magnesium synthetic rutile mother liquor by titanium and steel, comprising the following steps: Step 1: After the high-calcium and high-magnesium synthetic rutile mother liquor is filtered and concentrated, it enters a roasting furnace for roasting and recovery treatment. During the roasting treatment, the furnace temperature is set at 695 °C, the spraying flow rate is set at 3.95 m 3 / h, the air-coal ratio is set at 1.40, and the absorption tower flow rate is set at 3.95 m 3 / h. After roasting, a by-product of iron(III) oxide containing calcium and magnesium impurities and a preliminary hydrochloric acid product are obtained. The preliminary hydrochloric acid product coming out of the roasting furnace is successively passed through a double cyclone dust collector, a pre-concentrator, an absorption tower, and a washing tower to obtain a regenerated new hydrochloric acid with a mass concentration of 18.98%, and the HCl recovery rate is 99.34%; Step 2: The Fe2O3 by-product containing calcium and magnesium impurities obtained by roasting treatment in Step 1 is proportioned with vanadium-titanium iron concentrate at a ratio of 85% by mass to produce oxidized pellets. The roasting parameters are as follows: preheating temperature 830 °C, preheating time 13 min, roasting temperature 1300 °C, and roasting time 18 min. The compressive strength of the obtained oxidized pellets is 1757 / N·piece, and the mass content of TFe is 67.02%. The compressive strength is relatively low, affecting the blast furnace smelting effect.

[0032] In summary, the method for jointly treating high-calcium and high-magnesium synthetic rutile mother liquor by titanium and steel disclosed in the above embodiments of the present invention conducts high-temperature oxidation roasting treatment on the docking of the high-calcium and high-magnesium synthetic rutile mother liquor with the waste acid roasting device of the cold rolling pickling line of the steel plant. First, concentrated-absorbed hydrochloric acid is obtained for leaching titanium concentrate to prepare synthetic rutile or returning to the steel plate pickling line to pickle steel plates; second, by-products such as Fe2O3 containing certain calcium and magnesium impurity oxides are obtained, which are proportioned with vanadium-titanium iron concentrate at a certain ratio to produce oxidized pellets for use as blast furnace burden materials. Connecting the high-calcium and high-magnesium synthetic rutile mother liquor with the waste acid roasting device of the cold rolling pickling line of the steel plant for roasting treatment can efficiently realize the recycling of the high-calcium and high-magnesium synthetic rutile mother liquor to produce by-products such as hydrochloric acid and Fe2O3, effectively solve the problems of treatment and environmental protection of the high-calcium and high-magnesium synthetic rutile mother liquor and the high treatment cost, and also optimize the blast furnace burden structure to a certain extent.

[0033] So far, the embodiments of the present disclosure have been described in detail. To avoid obscuring the concept of the present disclosure, some details well known in the art have not been described. Those skilled in the art can fully understand how to implement the technical solutions disclosed herein based on the above description.

[0034] Although some specific embodiments of the present disclosure have been described in detail by way of examples, those skilled in the art should understand that the above examples are for illustrative purposes only and not for limiting the scope of the present disclosure. Those skilled in the art should understand that the above embodiments can be modified or equivalent substitutions can be made for some technical features without departing from the scope and spirit of the present disclosure. In particular, as long as there is no structural conflict, the technical features mentioned in each embodiment can be combined in any way.

Claims

1. A method for treating the mother liquor of high-calcium and high-magnesium artificial rutile by titanium-steel combined treatment, characterized in that, The artificial rutile mother liquor is subjected to high-temperature oxidation roasting treatment in the waste acid roasting device of the cold rolling pickling line to obtain a primary product of dilute hydrochloric acid and a by-product of iron(III) oxide containing calcium and magnesium impurities; the by-product of iron(III) oxide containing calcium and magnesium impurities is produced in proportion with vanadium-titanium iron concentrate to obtain oxidized pellets.

2. The method for treating the mother liquor of high-calcium and high-magnesium synthetic rutile by titanium-steel combined treatment according to claim 1, wherein During the high-temperature oxidation roasting treatment, the furnace temperature is 680 - 690 °C, the spraying flow rate is 2.80 - 2.90 m 3 / h, the air-coal ratio is 1.30 - 1.38, and the absorption tower flow rate is 3.70 - 3.80 m 3 / h.

3. The method for treating the mother liquor of high-calcium and high-magnesium artificial rutile by titanium-steel combined treatment according to claim 1, characterized in that, After the primary product of dilute hydrochloric acid is concentrated and absorbed, a regenerated new hydrochloric acid with a concentration greater than 19% is obtained.

4. The method for treating the mother liquor of high-calcium and high-magnesium artificial rutile by titanium-steel combined treatment according to claim 1, characterized in that, When the by-product of iron(III) oxide containing calcium and magnesium impurities is produced in proportion with vanadium-titanium iron concentrate to obtain oxidized pellets, the roasting parameters include: preheating temperature 780 °C - 820 °C, preheating time 8 - 12 min, roasting temperature 1250 - 1280 °C, and roasting time 13 - 17 min.

5. The method for treating the mother liquor of high-calcium and high-magnesium artificial rutile by titanium-steel combined treatment according to claim 1, wherein The obtained oxidized pellets have a compressive strength of 2481 - 3708 / N·piece.

6. The method for treating the mother liquor of high-calcium and high-magnesium artificial rutile by titanium-steel combined treatment according to claim 1, wherein In the obtained oxidized pellets, in terms of mass percentage, TFe is greater than 65.50%.

7. The method for treating the mother liquor of high-calcium and high-magnesium artificial rutile by titanium-steel combined treatment according to claim 1, characterized in that Before the artificial rutile mother liquor is subjected to high-temperature oxidation roasting treatment, it is first filtered and pre-concentrated.

8. The method for treating the mother liquor of high-calcium and high-magnesium artificial rutile by titanium-steel combined treatment according to claim 1, wherein After high-temperature oxidation roasting treatment, it passes through a double cyclone dust collector, a pre-concentrator, an absorption tower, and a washing tower in sequence to obtain a regenerated new hydrochloric acid with a concentration greater than 19%.

9. The method for treating the mother liquor of high-calcium and high-magnesium artificial rutile by titanium-steel combined treatment according to claim 1, characterized in that, The oxidized pellets are used as blast furnace burden.

10. The method for treating the mother liquor of high-calcium and high-magnesium artificial rutile by titanium-steel combined treatment according to claim 3, characterized in that, The regenerated new hydrochloric acid is used for leaching titanium concentrate to prepare artificial rutile, and / or the regenerated new hydrochloric acid is returned to the steel plate pickling line to pickle steel plates.

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