CN114229912A - System and process method for generating high-quality iron oxide powder and high-concentration hydrochloric acid - Google Patents
System and process method for generating high-quality iron oxide powder and high-concentration hydrochloric acid Download PDFInfo
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- CN114229912A CN114229912A CN202111558860.3A CN202111558860A CN114229912A CN 114229912 A CN114229912 A CN 114229912A CN 202111558860 A CN202111558860 A CN 202111558860A CN 114229912 A CN114229912 A CN 114229912A
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000000843 powder Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 23
- 239000003546 flue gas Substances 0.000 claims abstract description 92
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000002253 acid Substances 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000010521 absorption reaction Methods 0.000 claims abstract description 29
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000428 dust Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 238000005201 scrubbing Methods 0.000 claims description 15
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 12
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000008237 rinsing water Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000007770 graphite material Substances 0.000 claims description 4
- 239000000779 smoke Substances 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000000605 extraction Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 229960002089 ferrous chloride Drugs 0.000 description 4
- 238000007131 hydrochloric acid regeneration reaction Methods 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0009—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention provides a system for generating high-quality ferric oxide powder and high-concentration hydrochloric acid, which comprises a roasting furnace system, wherein the roasting furnace system comprises a roasting furnace, an acid gun is arranged at the top of the roasting furnace, a liquid outlet pipeline of a Venturi preconcentrator is communicated with the acid gun at the top of the roasting furnace, a double-cyclone dust collector is arranged on a flue gas pipeline communicated with the roasting furnace and the Venturi preconcentrator, at least one stage of flue gas cooler is arranged on a flue gas pipeline communicated with an absorption tower, the absorption tower is sequentially communicated with a Venturi washing tower and a washing tower through the flue gas pipeline, and the materials fed into the Venturi preconcentrator are FeCl which is extracted or purified and has very high purity3And (3) solution. The invention also provides aA process method for generating high-quality iron oxide powder and high-concentration hydrochloric acid.
Description
Technical Field
The invention relates to the industries and fields of mineral processing, wet metallurgy and the like, in particular to a system and a process method for generating high-quality iron oxide powder and high-concentration hydrochloric acid.
Background
In the mineral acid leaching process and the hydrometallurgy process, hydrochloric acid is often used, the hydrochloric acid with a certain concentration is used for acid leaching of the powdery mineral aggregate, and the hydrochloric acid and metal elements in the mineral aggregate are subjected to chemical reaction, so that the aim of dissolving the mineral aggregate in the hydrochloric acid is fulfilled. Removing solid particles from the solution after acid leaching through an impurity removal process, extracting through an extraction process section, and obtaining FeCl with very high purity from the back extract after extraction3And (3) solution. And this FeCl3After the solution is roasted by a spray roasting method, a high-purity iron oxide powder product can be prepared, as shown in figure 1.
With the development of the magnetic material industry, the price of iron oxide powder is continuously rising in recent years. Iron oxide powder in the market is basically a byproduct produced after waste acid generated by a pickling line in the steel industry is treated by a hydrochloric acid regeneration station, and the quality and purity of the iron oxide powder produced under the normal condition are not high due to the large impurity content in the waste acid of the pickling line. Even if a desiliconization system is provided, the quality of the produced iron powder is difficult to continuously meet the requirement of a special-grade product, and the specific surface area of the iron powder is low, so that the requirement of producing a high-end soft magnetic material cannot be met.
The ferric oxide powder is prepared by roasting the ferric chloride solution with higher purity after extraction, and the high-purity ferric oxide powder can be produced in principle, but no relevant engineering case report exists at present. The traditional hydrochloric acid regeneration process is to carry out regeneration treatment on waste acid generated by a pickling line in the steel industry, wherein the main component of the waste acid is a ferrous chloride solution.
It can be seen from the following chemical reaction equation that the ferrous chloride solution and the ferric chloride solution are slightly different in the roasting reaction process, except for the difference in reaction exotherm, reaction conditions, and the like, extra oxygen is required to participate in the reaction in the ferrous chloride solution reaction process, but not in the ferric chloride solution reaction process.
2FeCl2+2H2O+1/2O2＝Fe2O3+4HCl (1)
2FeCl3+3H2O＝Fe2O3+6HCl (2)
Under certain conditions, the following reactions can occur in the reaction furnace:
4HCl+O2＝2Cl2+2H2 (3)
equations (1) and (2), if the oxygen is excessive during the reaction, equation (3) occurs, resulting in the formation of a certain amount of chlorine gas in the system. Chlorine gas is strongly oxidizing and when encountering water, HClO is formed. Can generate strong oxidation effect on plastic equipment such as filler, plastic pipelines and the like in the tower, seriously influences the service life of the equipment, and even can generate environmental protection events.
Another key technique for calcining ferric chloride solution is to control the concentration of ferric chloride concentrate in the venturi preconcentrator. At a certain temperature, the solubility of ferric chloride and ferrous chloride is different, so that the concentration (density) of the concentrated ferric chloride solution circulating in the Venturi preconcentrator needs to be strictly controlled in the process of roasting the ferric chloride solution, and the ferric chloride solution can be crystallized in a pipeline due to poor control.
The key technology for generating high-concentration regenerated acid is that hydrochloric acid used by a pickling line in the normal steel industry and regenerated acid generated by a hydrochloric acid regeneration device are both 18 percent (equivalent to about 200 g/L), so that closed-loop circulation of the hydrochloric acid is formed. The concentration of hydrochloric acid required by the acid leaching or hydrometallurgy industry is generally 24-26%, which is higher than that of hydrochloric acid used by a conventional pickling line in the steel industry, so that the concentration of hydrochloric acid generated by the original process flow used in the steel industry cannot be directly used in an acid leaching or hydrometallurgy system. If the concentration of hydrochloric acid is increased by adding 32% concentrated hydrochloric acid to about 18% of the generated regenerated acid, the total volume of the hydrochloric acid in the system is increased. The hydrochloric acid absorption concentration is directly related to the temperature of the flue gas, and is influenced by the saturated vapor pressure in the flue gas, so that the temperature of a flue gas absorption process section must be reduced to increase the concentration of the regenerated acid.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a system and a process method for generating high-quality iron oxide powder and high-concentration hydrochloric acid, so as to solve the problems that the spray roasting method stably operates in the roasting process of ferric chloride solution, generates high-quality iron oxide powder and needs to produce high-concentration regenerated acid, and the invention at least solves part of the problems in the prior art.
The invention is realized by the following steps:
the invention provides a system for generating high-quality ferric oxide powder and high-concentration hydrochloric acid, which comprises a roasting furnace system, wherein the roasting furnace system comprises a roasting furnace, an acid gun is arranged at the top of the roasting furnace, a liquid outlet pipeline of a Venturi preconcentrator is communicated with the acid gun at the top of the roasting furnace, a double-cyclone dust collector is arranged on a flue gas pipeline communicated with the roasting furnace and the Venturi preconcentrator, at least one stage of flue gas cooler is arranged on a flue gas pipeline communicated with an absorption tower, the absorption tower is sequentially communicated with a Venturi washing tower and a washing tower through the flue gas pipeline, and the materials fed into the Venturi preconcentrator are FeCl which is extracted or purified and has very high purity3And (3) solution.
Furthermore, a flue gas oxygen content detector is also arranged on a flue gas pipeline communicated with the roasting furnace and the Venturi preconcentrator, and the flue gas oxygen content detector is arranged between the double-cyclone dust collector and the Venturi preconcentrator.
Furthermore, a Venturi circulating liquid density measuring device is arranged on a circulating pipeline of the Venturi preconcentrator.
Furthermore, a venturi circulating pump is arranged on a circulating pipeline of the venturi preconcentrator, a vertical pipeline is arranged at the outlet of the venturi circulating pump, and the venturi circulating liquid density measuring device comprises two pressure transmitters which are respectively arranged at different heights on the vertical pipeline.
Further, the system still includes the condensate water catch bowl, is equipped with one-level gas cooler and second grade gas cooler on the flue gas pipeline of venturi preconcentrator and absorption tower intercommunication, one-level gas cooler top and second grade gas cooler top all are equipped with the nozzle, the condensate water catch bowl passes through the condensate water and sprays pump and two the nozzle intercommunication, the condensate water export of one-level gas cooler bottom and the condensate water export of second grade gas cooler bottom all communicate with the condensate water catch bowl.
Furthermore, the heat exchange material of the primary flue gas cooler and the heat exchange material of the secondary flue gas cooler are both graphite materials.
Further, the system still includes cooling circulation water feeding pipe, one-level gas cooler and second grade gas cooler all communicate with cooling circulation water feeding pipe, and the system still includes cooling circulation return water pipe, one-level gas cooler and second grade gas cooler all communicate with cooling circulation return water pipe.
Further, the condensed water collection tank is communicated with a nozzle at the top of the absorption tower through an absorption tower feeding pump, and the bottom of the absorption tower is communicated with a regenerated acid liquid outlet pipe.
Further, the system also comprises FeCl2Solution inlet pipe and FeCl2A solution outlet pipe, the FeCl2Solution inlet pipe and FeCl2The solution outlet pipes are communicated with the Venturi scrubbing tower.
The invention also provides a process method for generating high-quality iron oxide powder and high-concentration hydrochloric acid, which comprises the following steps:
s1, starting a roasting furnace, a ferric oxide powder system and a double-cyclone dust remover;
s2, supplementing water to all towers, and starting all circulating pumps after the liquid level is reached;
s3, cooling circulating water for the primary flue gas cooler and the secondary flue gas cooler;
s4, starting a condensate spraying pump to flush the graphite block holes in the flue gas cooler;
s5, starting a combustion system of the roasting furnace; after the system is stable, carrying out rinsing water operation;
s6, after the rinsing water operation is stable, performing acid operation; FeCl3The solution enters a Venturi preconcentrator;
s7, after the production mode is switched to, the change of a Venturi circulating liquid density measuring device at the outlet of a circulating pump of the Venturi preconcentrator and a smoke oxygen content detector on a high-temperature smoke pipeline are controlled in a key mode;
s8 transferring system into FeCl3After the solution roasting mode is carried out for a period of time, the regenerated acid flows into a regenerated acid tank after the concentration of the regenerated acid is qualified by testing the regenerated acid at the liquid outlet of the absorption tower or setting a regenerated densimeter;
and S9, dropping the generated high-quality iron oxide powder from the bottom of the roasting furnace, and pumping the high-quality iron oxide powder into an iron oxide powder bin through an iron oxide powder conveying fan.
The invention has the following beneficial effects:
the invention can produce high-quality ferric oxide powder and generate high-concentration regenerated acid by roasting the ferric chloride solution with high purity after extraction, and has higher economic value. The sale price of high-quality iron oxide powder in the current market is about 2 ten thousand yuan, and the invention can generate good economic benefit.
In addition, the invention can ensure the stable operation of the system and the stable production of the equipment in the process of roasting the ferric chloride solution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a conventional iron oxide powder production process;
FIG. 2 is a schematic diagram of a system for producing high quality iron oxide powder and high concentration hydrochloric acid using ferric chloride solution according to an embodiment of the present invention;
FIG. 3 is an enlarged left side view of FIG. 2;
FIG. 4 is a first enlarged view of a portion of FIG. 3;
FIG. 5 is a second enlarged view of a portion of FIG. 3;
FIG. 6 is an enlarged view of the middle of FIG. 2;
FIG. 7 is an enlarged view of a portion of FIG. 6;
fig. 8 is an enlarged view of the right side of fig. 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1 to 8, a system for generating high-quality ferric oxide powder and high-concentration hydrochloric acid by using a ferric chloride solution according to an embodiment of the present invention includes a roasting furnace system, the ferric oxide powder system 2 includes a ferric oxide powder bin 21 and a ferric oxide powder packing machine 22, ferric oxide powder falling from the bottom of the roasting furnace 1 is pumped into the ferric oxide powder bin 21 by a ferric oxide powder conveying fan, the roasting furnace system includes a roasting furnace 1, a plurality of acid guns are disposed on the top of the roasting furnace 1, a liquid outlet pipeline of a venturi preconcentrator 4 is communicated with the acid guns on the top of the roasting furnace 1, a dual cyclone dust collector 3 is disposed on a flue gas pipeline communicating the roasting furnace 1 and the venturi preconcentrator 4, at least one stage of flue gas cooler is disposed on a flue gas pipeline communicating the venturi preconcentrator 4 with an absorption tower 7, the absorption tower 7 is sequentially communicated with a venturi washing tower 8 and a washing tower 11 by the flue gas pipeline, the material fed into the Venturi preconcentrator is FeCl with very high purity after extraction or purification3And (3) solution. The concentrated acid is converted into an atomized state by an acid gun and sprayed into the roasting furnace 1, and the acid gun is cleaned by desalted water 20. The gas 23 supply duct and the air 24 supply duct are both in communication with the roasting furnace 1. FeCl3The solution 25 supply line and the rinse water supply line 26 are both in communication with the venturi preconcentrator 4.
A flue gas oxygen content detector 18 is also arranged on a flue gas pipeline communicated with the roasting furnace 1 and the Venturi preconcentrator 4, and the flue gas oxygen content detector 18 is arranged between the double cyclone dust collector 3 and the Venturi preconcentrator 4.
The circulating pipeline of the Venturi preconcentrator 4 is provided with a Venturi circulating liquid density measuring device 19. The circulating pipeline of the venturi preconcentrator 4 is provided with a venturi circulating pump, the outlet of the venturi circulating pump is provided with a vertical pipeline, the venturi circulating liquid density measuring device 19 comprises two pressure transmitters (such as P1 and P2 in figure 5), and the two pressure transmitters are respectively arranged at different heights on the vertical pipeline.
The system still includes condensate collection tank 14, is equipped with one-level gas cooler 5 and second grade gas cooler 6 on the flue gas pipeline of venturi preconcentrator 4 and absorption tower 7 intercommunication, 5 tops of one-level gas cooler and 6 tops of second grade gas cooler all are equipped with the nozzle, condensate collection tank 14 passes through condensate spray pump 13 and two the nozzle intercommunication. The nozzle adopts graphite nozzle or carborundum nozzle, and the nozzle can be used to wash the dust that adheres in the tube side, can also absorb the HCl in the flue gas through spraying. And a condensed water outlet at the bottom of the primary flue gas cooler 5 and a condensed water outlet at the bottom of the secondary flue gas cooler 6 are communicated with a condensed water collecting tank 14. The heat exchange material of the primary flue gas cooler 5 and the heat exchange material of the secondary flue gas cooler 6 are both graphite materials.
The system further comprises a cooling circulation water supply 28 pipeline, the primary flue gas cooler 5 and the secondary flue gas cooler 6 are communicated with the cooling circulation water supply 28 pipeline, the system further comprises a cooling circulation water return 27 pipeline, and the primary flue gas cooler 5 and the secondary flue gas cooler 6 are communicated with the cooling circulation water return 27 pipeline. The heat exchanger (flue gas cooler) adopts circulating cooling water to exchange heat, and removes heat in the system, thereby achieving the purpose of cooling.
The condensed water collecting tank 14 is communicated with a nozzle at the top of the absorption tower 7 through an absorption tower feed pump 15, and the bottom of the absorption tower 7 is communicated with a regenerated acid 29 liquid outlet pipe and a rinsing water 26 liquid outlet pipe.
The system also includes FeCl2Solution inlet pipe and FeCl2A solution outlet pipe, the FeCl2Solution inlet pipe and FeCl2The solution outlet pipes are communicated with a Venturi scrubbing tower 8, and a Venturi scrubbing tower circulating pump 16 is arranged on a circulating pipeline of the Venturi scrubbing tower 8.
The flue gas pipeline that venturi scrubber 8 and scrubbing tower 11 communicate is equipped with waste gas fan 9 and horizontal liquid drop separator 10 on, 20 moisturizing pipes of scrubbing tower 11 intercommunication desalinized water, and the nozzle intercommunication at scrubbing tower 11 bottom liquid outlet through scrubbing tower circulating pump 17 and scrubbing tower 11 top, and scrubbing tower 11 bottom liquid outlet passes through scrubbing tower circulating pump 17 and condensate water collection tank 14 intercommunication.
The invention provides a process and an operation method for generating high-quality iron oxide powder and high-concentration hydrochloric acid by using an iron chloride solution.
The invention discloses a process based on simulation by AspenPlus software according to the reaction principle in the background technology and by combining the principle and the characteristics of the chemical reaction.
The process comprises the following equipment, wherein a roasting furnace system (comprising a roasting furnace 1, an acid gun device and a combustion system), an iron oxide powder system 2, a double-cyclone dust collector 3, a Venturi preconcentrator 4, a primary flue gas cooler 5, a secondary flue gas cooler 6, an absorption tower 7, a Venturi washing tower 8, a waste gas fan 9, a horizontal liquid drop separator 10, a washing tower 11, a chimney 12, a condensate spraying pump 13, a condensed water collecting tank 14, an absorption tower feeding pump 15, a Venturi washing tower circulating pump 16, a washing tower circulating pump 17, a flue gas oxygen content detector 18, a Venturi circulating liquid density measuring device 19 and the like.
Also shown in fig. 2 are: 20, desalted water; an iron oxide powder bin 21; an iron oxide powder packing machine 22; a fuel gas 23; air 24; FeCl3A solution 25; rinse water 26; cooling circulating return water 27; cooling circulating feedwater 28; a regenerating acid 29; spent acid 30 (FeCl)2A solution).
Wherein, the roasting furnace system (comprising the roasting furnace 1, the acid gun device and the combustion system), the ferric oxide powder system 2 and the double-cyclone dust remover 3 are basically the same as the traditional hydrochloric acid regeneration process. And will not be described in too much detail.
In view of the above background art, in the chemical reaction formula (2), oxygen is not needed, and oxidation of subsequent equipment and packing due to excessive oxygen is avoided, the system is provided with a set of flue gas oxygen content detector 18 on the high-temperature flue gas pipeline in front of the venturi preconcentrator 4. The analyzer can detect the concentration of oxygen in the flue gas, so that the content of oxygen in the flue gas is changed by adjusting the air-coal ratio (the mass ratio between air and fuel gas) of a combustion system, and the adverse effect on subsequent equipment caused by excessive oxygen in the flue gas is avoided.
In view of the fact that the above-mentioned ferric chloride solution crystallizes due to its solubility after concentration in the venturi preconcentrator 4, a method of online monitoring the density, i.e. a venturi circulating liquid density measuring device 19, is provided. The venturi circulating liquid density measuring device 19 is composed of two pressure transmitters, which are respectively installed at different heights of the vertical pipeline at the outlet of the venturi circulating pump, and the density of the solution is calculated according to the pressure value measured by the pressure transmitters and the difference value of the installation heights. Thereby realizing the real-time detection of the density of the concentrated ferric chloride solution in the pipeline.
For obtaining the high-concentration regenerated hydrochloric acid solution, the flue gas enters the first-stage flue gas cooler 5 and the second-stage flue gas cooler 6 after passing through the venturi preconcentrator 4, the heat exchange material of the first-stage flue gas cooler 5 and the heat exchange material of the second-stage flue gas cooler 6 are both graphite materials, and the flue gas contains a certain amount of dust and can be adhered to the inner wall of the first-stage flue gas cooler 5 and the inner wall of the second-stage flue gas cooler 6. The invention arranges nozzles on the top of the primary flue gas cooler 5 and the top of the secondary flue gas cooler 6, the nozzle can be made of graphite or silicon carbide, or PVDF and other hydrochloric acid resistant and high temperature resistant materials; the spray nozzle can be used for washing dust adhered to the tube pass, and HCl in the flue gas can be absorbed by spraying. The heat exchanger (flue gas cooler) adopts circulating cooling water to exchange heat, and removes heat in the system, thereby achieving the purpose of cooling. The condensed water from the cooling process of the flue gas enters a condensed water collection tank 14 (rinsing water collection tank), which contains a certain amount of HCl, which can be mixed with dust (Fe)2O3) The reaction is carried out. The cooling liquid spraying pump 13 lifts the condensed liquid to the nozzle of the cooler to spray the graphite blocks in the tower, so that block holes are prevented from being blocked.
After two-stage heat exchange, the temperature of the flue gas can be reduced to a lower temperature (40-42 ℃), and the flue gas with the temperature reduced according to the saturated steam partial pressure enters the absorption tower 7, so that hydrochloric acid with higher concentration is obtained. It is theoretically calculated that a concentration of about 25-26% of the regenerated acid can be obtained. The hydrochloric acid with higher concentration can be directly used in the process stages of acid leaching, wet metallurgy and the like, thereby achieving the purpose of closed loop circulation.
After passing through the absorption tower 7, the flue gas enters a venturi scrubber 8 for avoiding Cl in the flue gas2Oxidizing subsequent filler and plastic tower with strong oxidizing substances such as HClO, and introducing FeCl with a certain concentration into the Venturi scrubbing tower 82Solution of Fe2+Has reducibility and can carry out oxidation-reduction reaction with oxides in the flue gas. Thereby eliminating Cl in the flue gas2And strong oxidizing substances such as HClO.
The flue gas after passing through the venturi scrubber 8 is pumped into a final scrubber 11 through a waste gas fan 9, and the water used for supplementing the scrubber 11 is desalted water.
The second embodiment of the invention provides a process method for generating high-quality iron oxide powder and high-concentration hydrochloric acid, which comprises the following steps:
1. the roasting furnace 1, the ferric oxide powder system 2 and the double-cyclone dust remover 3 are started.
2. And (5) supplementing water to all the towers, and starting all the circulating pumps after the liquid level is reached.
3. Cooling circulating water is supplied to the first-stage flue gas cooler 5 and the second-stage flue gas cooler 6.
4. And (4) starting a condensate spray pump 13 to flush the graphite block holes in the graphite heat exchanger (flue gas cooler).
5. Starting a combustion system of the roasting furnace; after the system stabilized, a rinse water operation was performed.
6. After the operation of rinsing water is stable, performing acid operation; FeCl3The solution enters the venturi preconcentrator 4 and is switched to the production mode.
7. Differential pressure densitometer (venturi circulating fluid density measuring device 19) with emphasis on controlling circulating pump outlet of venturi preconcentratorA flue gas oxygen content detector 18 on the chemical and high temperature flue gas pipeline. The automatic control system can control the FeCl according to the change of the differential pressure densimeter3The liquid inlet amount of the solution is adjusted, the combustion air flow of the combustion system can be automatically adjusted according to the flue gas oxygen content detector 18 on the high-temperature flue gas pipeline, and the control system adopts the prior art. And normal and safe production of the system is ensured.
8. Systematic transfer into FeCl3After the solution roasting mode is carried out for a period of time, the regenerated acid flows into a regenerated acid tank after the concentration of the regenerated acid is qualified by testing the regenerated acid at the liquid outlet of the absorption tower 7 or setting a regenerated densimeter.
9. The generated high-quality iron oxide powder falls from the bottom of the roasting furnace 1 and is pumped into an iron oxide powder bin through an iron oxide powder conveying fan.
The method is suitable for acid liquor generated by dissolving powder substances with hydrochloric acid, and ferric chloride solution with high purity is obtained through impurity removal and purification and an extraction process. Under certain reaction conditions, the ferric chloride solution is subjected to high-temperature pyrohydrolysis reaction, so that high-quality ferric oxide powder is produced. The powder can be fly ash, mica ore, rich iron ore, ilmenite and the like.
Details not described in this specification are within the skill of the art that are well known to those skilled in the art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A system for generating high-quality iron oxide powder and high-concentration hydrochloric acid is characterized in that: the system comprises a roasting furnace system, wherein the roasting furnace system comprises a roasting furnace, an acid gun is arranged at the top of the roasting furnace, a liquid outlet pipeline of a Venturi preconcentrator is communicated with the acid gun at the top of the roasting furnace, a double-cyclone dust collector is arranged on a flue gas pipeline communicated with the roasting furnace and the Venturi preconcentrator, at least one stage of flue gas cooler is arranged on a flue gas pipeline communicated with an absorption tower of the Venturi preconcentrator, and the absorption tower is provided with a flue gas inlet and a flue gas outletThe tower is communicated with a Venturi scrubbing tower and a scrubbing tower in sequence through a flue gas pipeline, and the materials fed into the Venturi preconcentrator are FeCl which is extracted or purified and has very high purity3And (3) solution.
2. The system for producing high quality iron oxide powder and high concentration hydrochloric acid as claimed in claim 1, wherein: and a flue gas oxygen content detector is also arranged on a flue gas pipeline communicated with the roasting furnace and the Venturi preconcentrator and is arranged between the double-cyclone dust collector and the Venturi preconcentrator.
3. The system for producing high quality iron oxide powder and high concentration hydrochloric acid as claimed in claim 1, wherein: and a Venturi circulating liquid density measuring device is arranged on a circulating pipeline of the Venturi preconcentrator.
4. A system for producing high quality iron oxide powder and high concentration hydrochloric acid as claimed in claim 3 wherein: the circulating pipeline of the Venturi preconcentrator is provided with a Venturi circulating pump, the outlet of the Venturi circulating pump is provided with a vertical pipeline, and the Venturi circulating liquid density measuring device comprises two pressure transmitters which are arranged at different heights on the vertical pipeline respectively.
5. The system for producing high quality iron oxide powder and high concentration hydrochloric acid as claimed in claim 1, wherein: the system still includes the condensate water collecting tank, is equipped with one-level gas cooler and second grade gas cooler on the flue gas pipeline of venturi preconcentrator and absorption tower intercommunication, one-level gas cooler top and second grade gas cooler top all are equipped with the nozzle, the condensate water collecting tank passes through the condensate water and sprays pump and two the nozzle intercommunication, the condensate water export of one-level gas cooler bottom and the condensate water export of second grade gas cooler bottom all communicate with the condensate water collecting tank.
6. The system for producing high quality iron oxide powder and high concentration hydrochloric acid as claimed in claim 5, wherein: the heat exchange material of the primary flue gas cooler and the heat exchange material of the secondary flue gas cooler are both graphite materials.
7. The system for producing high quality iron oxide powder and high concentration hydrochloric acid as claimed in claim 5, wherein: the system further comprises a cooling circulation water feeding pipeline, the first-stage flue gas cooler and the second-stage flue gas cooler are communicated with the cooling circulation water feeding pipeline, the system further comprises a cooling circulation water return pipeline, and the first-stage flue gas cooler and the second-stage flue gas cooler are communicated with the cooling circulation water return pipeline.
8. The system for producing high quality iron oxide powder and high concentration hydrochloric acid as claimed in claim 5, wherein: the condensed water collection tank is communicated with a nozzle at the top of the absorption tower through an absorption tower feeding pump, and the bottom of the absorption tower is communicated with a regenerated acid liquid outlet pipe.
9. The system for producing high quality iron oxide powder and high concentration hydrochloric acid as claimed in claim 1, wherein: the system also includes FeCl2Solution inlet pipe and FeCl2A solution outlet pipe, the FeCl2Solution inlet pipe and FeCl2The solution outlet pipes are communicated with the Venturi scrubbing tower.
10. A process method for generating high-quality iron oxide powder and high-concentration hydrochloric acid is characterized by comprising the following steps:
s1, starting a roasting furnace, a ferric oxide powder system and a double-cyclone dust remover;
s2, supplementing water to all towers, and starting all circulating pumps after the liquid level is reached;
s3, cooling circulating water for the primary flue gas cooler and the secondary flue gas cooler;
s4, starting a condensate spraying pump to flush the graphite block holes in the flue gas cooler;
s5, starting a combustion system of the roasting furnace; after the system is stable, carrying out rinsing water operation;
s6, stabilizing the rinsing waterAfter that, the acid operation is carried out; FeCl3The solution enters a Venturi preconcentrator;
s7, after the production mode is switched to, the change of a Venturi circulating liquid density measuring device at the outlet of a circulating pump of the Venturi preconcentrator and a smoke oxygen content detector on a high-temperature smoke pipeline are controlled in a key mode;
s8 transferring system into FeCl3After the solution roasting mode is carried out for a period of time, the regenerated acid flows into a regenerated acid tank after the concentration of the regenerated acid is qualified by testing the regenerated acid at the liquid outlet of the absorption tower or setting a regenerated densimeter;
and S9, dropping the generated high-quality iron oxide powder from the bottom of the roasting furnace, and pumping the high-quality iron oxide powder into an iron oxide powder bin through an iron oxide powder conveying fan.
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