CN102586595B - Acid leaching method of vanadium-containing shale - Google Patents
Acid leaching method of vanadium-containing shale Download PDFInfo
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- CN102586595B CN102586595B CN2012100432538A CN201210043253A CN102586595B CN 102586595 B CN102586595 B CN 102586595B CN 2012100432538 A CN2012100432538 A CN 2012100432538A CN 201210043253 A CN201210043253 A CN 201210043253A CN 102586595 B CN102586595 B CN 102586595B
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Abstract
The invention relates to an acid leaching method of vanadium-containing shale. In the invention, n acid leaching units for vanadium-containing shale are in series connection, i.e., liquid inlet pipe (9) of each unit is connected with overflow pipe (2) of previous unit, and overflow pipe (2) of each unit is connected with liquid inlet pipe (9) of next unit, to realize continuous production of acid leaching process; n-stage n-time acid leaching and one-time water washing are adopted, n is 3-6. The acid leaching process comprises stirring calcine and acid leaching solution at solid/liquid mass ratio of 1:(1.5-3) at 90-100 DEG C and 150-999 rpm for 30-75 min in corresponding acid leaching unit, and standing for 5-10 min. The first-stage leaching solution is 15-35% sulfuric acid solution, and the second-stage first-time to n-stage nth-time leaching solution is acid leaching solution and washing water from previous stage, so as to realize cyclic utilization of sulfuric acid solution and other acid leaching solution besides qualified acid leaching solution. The invention has the merits of simple process, low acid consumption, high vanadium leaching rate, and continuous production. The acid leaching solution satisfies requirement of subsequent extraction process.
Description
Technical field
The invention belongs to and contain vanadium shale hydrometallurgy vanadium extraction technical field, be specifically related to a kind of acidleach method that contains vanadium shale.
Background technology
Contain in vanadium shale process for extracting vanadium flow process, leaching is indispensable operation, will contain in the solution such as vanadium in vanadium shale is water-soluble, sour, alkali, is convenient to next step enriching and recovering.Wherein acid-leaching vanadium-extracted application is comparatively extensive, in existing acid leaching process flow process, single-stage acid leaching process, secondary acid leaching process and multistage acid leaching process is arranged.
The single-stage acid leaching process (Ma Shiqiang, process for extracting vanadium from stone coal is commented. Hunan non-ferrous metal, 1998,14 (4): 21～24) have that the pickling agent consumption is large, vanadic acid soaks that rate is low, the defectives such as subsequent technique requirement can not be directly satisfied in pickling liquor.
Secondary acid leaching process (Lu Zhaoling, extract experimental study and the industrial practice of Vanadium Pentoxide in FLAKES from bone coal with acid system. hydrometallurgy, 2002,21 (4): 178～179.WANG Mingyu, XIAO Liansheng, LI Qinggang.Leaching ofvanadium from stone coal with sulfuric acid.Rare metals, 2009,18 (1): have 1～4) that the pH value of final pickling liquor low can not satisfy that subsequent job requires, leaching time is long, energy consumption is high, vanadic acid soaks rate less than the defective such as 80%.
multistage acid leaching process, a kind of is heap leaching method, and the shortcoming of this technique is that working cycle is long, and floor space is large, and environmental problem is serious, another kind is that the multi-stage countercurrent stirring technique is as " reclaiming the method for vanadium from contain navajoite stone " (US No4666512) patented technology, " a kind of method of segmentation formic acid circulation acidleach coarse particles in laterite nickel ores " be patented technology (CN200810072530.1), " method and apparatus of the countercurrent fluidized acidleach chromite of continuous multi-stage basic roasting grog " (85100396) and " a kind of multi-stage countercurrent acidleach method " (CN 1189389A), this technique exists the acidleach process not carry out continuously, pickling equipment need be used in conjunction with to realize with worm conveyor and lift the process of solid-liquid separation and transportation pickling liquor and acid leaching residue, complex process, working cycle is long, corresponding utility appliance is the shortcoming such as acid-alkali-corrosive-resisting not.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, purpose is to provide that simple, the sour consumption of a kind of technique is low, vanadic acid soak rate high, can produce continuously and pickling liquor can be satisfied the acidleach method that contains vanadium shale of subsequent technique requirement.
For achieving the above object, the method that the present invention adopts is: be n and contain vanadium shale pickling equipment series connection use aspect equipment, the liquid-inlet pipe that is each described pickling equipment is connected with the upflow tube of its upper level pickling equipment, and the upflow tube of each described pickling equipment is connected with the liquid-inlet pipe of its next stage pickling equipment; Be n acidleach of n level and once washing at process aspect, n is 3～6.Concrete grammar is as follows:
First step acidleach is to carry out an acidleach and once washing in first contains vanadium shale pickling equipment
First will contain vanadium shale calcining and sulphuric acid soln is 1 by the solid-liquid mass ratio: mix in first contains vanadium shale pickling equipment (1.5～3), carry out again the one-level acidleach, the primary acids soaking technology is: be that 90～100 ℃ and sand pump rotating speed are to stir 30～75min, standing 5～10min under the condition of 150～999r/min in temperature.
After the one-level acidleach finishes, first open the first surplus valve that contains vanadium shale pickling equipment and discharge the primary acids immersion liquid, the primary acids immersion liquid is sent to the second liquid storing pool that contains vanadium shale pickling equipment or primary acids immersion liquid through water pump, again the first one-level acid leaching residue that contains in vanadium shale pickling equipment is washed, one-level acid leaching residue after washing is sent into Tailings Dam, and the one-level wash water after washing is sent to second and contains vanadium shale pickling equipment or one-level water washing tank.
Second stage acidleach is to carry out secondary pickling and once washing in second contains vanadium shale pickling equipment
To contain vanadium shale calcining and primary acids immersion liquid is 1 by the solid-liquid mass ratio: mix in second contains vanadium shale pickling equipment (1.5～3), then carry out an acidleach of secondary, and acid leaching process of secondary is with the one-level acid leaching process;
After an acidleach of secondary finishes, open the second surplus valve that contains vanadium shale pickling equipment and discharge a pickling liquor of secondary, a pickling liquor of secondary is sent into the 3rd liquid storage tank that contains vanadium shale pickling equipment or a pickling liquor of secondary through water pump;
Then contain one-level wash water in vanadium shale pickling equipment with addition of sulfuric acid to entering second, mix with second acid leaching residue of secondary that contains in vanadium shale pickling equipment, carry out the secondary secondary pickling, secondary secondary pickling technique is with the one-level acid leaching process;
After the secondary secondary pickling finishes, first open the second surplus valve that contains vanadium shale pickling equipment and discharge the immersion liquid of secondary quadratic acid, the immersion liquid of secondary quadratic acid is sent to the 3rd liquid storage tank that contains vanadium shale pickling equipment or the immersion liquid of secondary quadratic acid through water pump; The second secondary secondary pickling slag that contains in vanadium shale pickling equipment is washed again, the secondary secondary pickling slag after washing is sent into Tailings Dam, the secondary wash water after washing is sent to the 3rd and contains vanadium shale pickling equipment or secondary water washing tank;
Third stage acidleach is to carry out three acidleach and once washing in the 3rd contains vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and secondary is 1 by the solid-liquid mass ratio: mix in the 3rd contains vanadium shale pickling equipment (1.5～3), then carry out three grades of acidleach, and three grades of acid leaching process are with the one-level acid leaching process;
After three grades of acidleach finish, open the 3rd surplus valve that contains vanadium shale pickling equipment and discharge three grades of pickling liquors, three grades of pickling liquors are sent into the 4th liquid storage tank that contains vanadium shale pickling equipment or three grades of pickling liquors through water pump;
Three grades of acid leaching residues that secondary quadratic acid immersion liquid and the 3rd contains in vanadium shale pickling equipment mix, and carry out three grades of secondary picklings, and three grades of secondary pickling techniques are with the one-level acid leaching process;
After three grades of secondary picklings finish, open the 3rd surplus valve that contains vanadium shale pickling equipment and discharge three grades of quadratic acid immersion liquid, three grades of quadratic acid immersion liquid are sent into the 4th liquid storage tank that contains vanadium shale pickling equipment or three grades of quadratic acid immersion liquid through water pump;
Then contain secondary wash water in vanadium shale pickling equipment with addition of sulfuric acid to entering the 3rd, mix with the 3rd three grades of secondary pickling slags that contain in vanadium shale pickling equipment, carry out three grades of three acidleach, the three grades of same level of three acid leaching process acid leaching process;
After three grades of three acidleach finish, first open the 3rd surplus valve that contains vanadium shale pickling equipment and discharge three grades of three pickling liquors, three grades of three pickling liquors are sent to the 4th liquid storage tank that contains vanadium shale pickling equipment or three grades of three pickling liquors through water pump; The 3rd three grades of three acid leaching residues that contain in vanadium shale pickling equipment are washed again, three grades of three acid leaching residues after washing are sent into Tailings Dam, three grades of wash waters after washing are sent to the 4th and contain vanadium shale pickling equipment or three grades of water washing tanks;
……；
The acidleach of n level is to contain at n to carry out n acidleach and once washing in vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and n-1 level is 1 by the solid-liquid mass ratio: (1.5～3) contain in vanadium shale pickling equipment at n and mix, then carry out an acidleach of n level, and acid leaching process of n level is with the one-level acid leaching process;
After an acidleach of n level finishes, open the pickling liquor of surplus valve discharge n level that n contains vanadium shale pickling equipment, a pickling liquor of n level is qualified pickling liquor, is sent to the liquid storage tank of a pickling liquor of n level, is ready for use on the extraction operation;
The immersion liquid of n-1 level quadratic acid mixes with acid leaching residue of n level in n contains vanadium shale pickling equipment again, carries out n level secondary pickling, and n level secondary pickling technique is with the one-level acid leaching process;
After n level secondary pickling finishes, open the surplus valve that n contains vanadium shale pickling equipment and discharge the immersion liquid of n level quadratic acid, it is standby that the liquid storage tank of n level quadratic acid immersion liquid is sent in the immersion liquid of n level quadratic acid;
……；
N-1 pickling liquor of n-1 level contains interior n-2 the acid leaching residue of n level of vanadium shale pickling equipment with n and mixes, and carries out n-1 acidleach of n level, the same level of n-1 acid leaching process of n level acid leaching process;
After n-1 acidleach of n level finishes, open the surplus valve that n contains vanadium shale pickling equipment and discharge n-1 pickling liquor of n level, it is standby that the liquid storage tank of n-1 pickling liquor of n level is sent in n-1 pickling liquor of n level;
Then contain n-1 level wash water in vanadium shale pickling equipment with addition of sulfuric acid to entering n, mix with n-1 acid leaching residue of n level in n contains vanadium shale pickling equipment, carry out n acidleach of n level, the same level of n acid leaching process of n level acid leaching process;
After n acidleach of n level finishes, first open n the pickling liquor of surplus valve discharge n level that n contains vanadium shale pickling equipment, n pickling liquor of n level is standby through the liquid storage tank that water pump is sent to n pickling liquor of n level; N the acid leaching residue of n level that again n is contained in vanadium shale pickling equipment washed, and n the acid leaching residue of n level after washing sent into Tailings Dam, and it is standby that the n level wash water after washing is sent to n level water washing tank.
In technique scheme: the described vanadium shale calcining that contains is to contain vanadium shale raw ore prepared calcining after oxidizing roasting, contains the V of vanadium shale calcining
2O
5Grade is 0.6～1.2wt%; The volumetric concentration of described sulphuric acid soln is 15～35%; Describedly be 8～15% of the wash water volume that mixes with this sulfuric acid with addition of sulfuric acid with addition of amount.
Described first contain vanadium shale pickling equipment, second contain vanadium shale pickling equipment ... contain vanadium shale pickling equipment with n and be " a kind of pickling equipment be used to containing vanadium shale " patent of invention technology that the applicant applies on the same day, the concrete structure of this pickling equipment comprises cell body, upper cover plate, upflow tube, ore pulp circulation tube, liquid-inlet pipe and drainage conduit.
The top of cell body is hollow round table I, and the middle part is hollow cylinder I, and the bottom is hollow round table II, and the bottom is hollow cylinder II, and the diameter of the lower port diameter of hollow round table I and hollow cylinder I is identical with the back cut diameter of hollow round table II; The hollow round table I of cell body is fixedly connected with upper cover plate by bolt, and upper cover plate is provided with opening for feed; The top of the hollow cylinder I of cell body is connected with upflow tube and ore pulp circulation tube, and upflow tube is equipped with surplus valve and water pump, liquid-inlet pipe or the external liquid storage tank of upflow tube external subordinate pickling equipment.
The lower end of ore pulp circulation tube communicates with the bottom of the hollow round table II of cell body, and the ore pulp circulation tube is equipped with sand pump; The hollow cylinder II of cell body is provided with liquid-inlet pipe and steam port, the upflow tube of the external higher level's pickling equipment of liquid-inlet pipe or external storage acid pond, and the lower end of hollow cylinder II is provided with drainage conduit, and drainage conduit is equipped with butterfly valve.
Owing to adopting technique scheme, the present invention adopts the patent of invention technology of " a kind of pickling equipment be used to containing vanadium shale " that the applicant applies on the same day aspect equipment, n " a kind of pickling equipment be used to containing vanadium shale " series connection is used, be that each equipment liquid-inlet pipe is connected with upper level equipment upflow tube, each equipment upflow tube is connected with next stage equipment liquid-inlet pipe, has realized the continuous production of acid leaching process; Adopt n acidleach of n level and a water-washing technique at process aspect,, technological process is simple; Through n acidleach of n level with after once washing, the final pickling liquor of gained contains the requirement that vanadium concentration and pH value all satisfy follow-up extraction process, realize the recycle of sulphuric acid soln and other pickling liquor except qualified pickling liquor, reduced sour consumption, significantly reduced production cost; Contain vanadium shale pickling equipment by the mode that steam heating stirs, make the acidleach temperature reach 90～100 ℃, strengthened the chemical reaction of acid-leaching vanadium-extracted process, the vanadic acid rate of soaking reaches more than 88%.
Therefore, the characteristics that the present invention has that simple, the sour consumption of technique is low, V leaching rate is high, follow-up extraction process requirement is satisfied in continuous production, pickling liquor.
Description of drawings
Fig. 1 is a kind of process flow sheet of the present invention.
Fig. 2 is a kind of equipment schematic diagram of the present invention.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments, is not the restriction to its protection domain.
For avoiding repetition, the existing technical parameter unification that this embodiment is related is described below: containing vanadium shale calcining is to contain vanadium shale raw ore prepared calcining after oxidizing roasting, contains the V of vanadium shale calcining
2O
5Grade is 0.6～1.2wt%; The volumetric concentration of sulphuric acid soln is 15～35%; Be 8～15% of the wash water volume that mixes with this sulfuric acid with addition of sulfuric acid with addition of amount.Repeat no more in specific embodiment.
A kind of acidleach method that contains vanadium shale, be 4 and contain vanadium shale pickling equipment series connection use aspect equipment, the liquid-inlet pipe 9 that is each described pickling equipment is connected with the upflow tube 2 of its upper level pickling equipment, and the upflow tube 2 of each described pickling equipment is connected with the liquid-inlet pipe 9 of its next stage pickling equipment; Be four acidleach of level Four and once washing at process aspect, concrete grammar is as shown in Figure 1:
First step acidleach is to carry out an acidleach and once washing in first contains vanadium shale pickling equipment
First will contain vanadium shale calcining and sulphuric acid soln is 1 by the solid-liquid mass ratio: mix in first contains vanadium shale pickling equipment (1.5～2), carry out again the one-level acidleach, the primary acids soaking technology is: be that 90～100 ℃ and sand pump 10 rotating speeds are to stir 45～60min, standing 5～10min under the condition of 700～999r/min in temperature.
After the one-level acidleach finishes, first open the first surplus valve 3 that contains vanadium shale pickling equipment and discharge the primary acids immersion liquid, the primary acids immersion liquid is sent to the second liquid storing pool that contains vanadium shale pickling equipment or primary acids immersion liquid through water pump 6, again the first one-level acid leaching residue that contains in vanadium shale pickling equipment is washed, one-level acid leaching residue after washing is sent into Tailings Dam, and the one-level wash water after washing is sent to second and contains vanadium shale pickling equipment or one-level water washing tank.
Second stage acidleach is to carry out secondary pickling and once washing in second contains vanadium shale pickling equipment
To contain vanadium shale calcining and primary acids immersion liquid is 1 by the solid-liquid mass ratio: mix in second contains vanadium shale pickling equipment (1.5～2), then carry out an acidleach of secondary, and acid leaching process of secondary is with the one-level acid leaching process.
After an acidleach of secondary finishes, open the second surplus valve 3 that contains vanadium shale pickling equipment and discharge a pickling liquor of secondarys, a pickling liquor of secondary is sent into the 3rd liquid storage tank that contains vanadium shale pickling equipment or a pickling liquor of secondary through water pump 6.
Then contain one-level wash water in vanadium shale pickling equipment with addition of sulfuric acid to entering second, mix with second acid leaching residue of secondary that contains in vanadium shale pickling equipment, carry out the secondary secondary pickling, secondary secondary pickling technique is with the one-level acid leaching process.
After the secondary secondary pickling finishes, first open the second surplus valve 3 that contains vanadium shale pickling equipment and discharge the immersion liquid of secondary quadratic acid, the immersion liquid of secondary quadratic acid is sent to the 3rd liquid storage tank that contains vanadium shale pickling equipment or the immersion liquid of secondary quadratic acid through water pump 6; The second secondary secondary pickling slag that contains in vanadium shale pickling equipment is washed again, the secondary secondary pickling slag after washing is sent into Tailings Dam, the secondary wash water after washing is sent to the 3rd and contains vanadium shale pickling equipment or secondary water washing tank.
Third stage acidleach is to carry out three acidleach and once washing in the 3rd contains vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and secondary is 1 by the solid-liquid mass ratio: mix in the 3rd contains vanadium shale pickling equipment (1.5～2), then carry out three grades of acidleach, and three grades of acid leaching process are with the one-level acid leaching process.
After three grades of acidleach finish, open the 3rd surplus valve 3 that contains vanadium shale pickling equipment and discharge three grades of pickling liquors, three grades of pickling liquors are sent into the 4th liquid storage tank that contains vanadium shale pickling equipment or three grades of pickling liquors through water pump 6.
Three grades of acid leaching residues that secondary quadratic acid immersion liquid and the 3rd contains in vanadium shale pickling equipment mix, and carry out three grades of secondary picklings, and three grades of secondary pickling techniques are with the one-level acid leaching process.
After three grades of secondary picklings finish, open the 3rd surplus valve 3 that contains vanadium shale pickling equipment and discharge three grades of quadratic acid immersion liquid, three grades of quadratic acid immersion liquid are sent into the 4th liquid storage tank that contains vanadium shale pickling equipment or three grades of quadratic acid immersion liquid through water pump 6.
Then contain secondary wash water in vanadium shale pickling equipment with addition of sulfuric acid to entering the 3rd, mix with the 3rd three grades of secondary pickling slags that contain in vanadium shale pickling equipment, carry out three grades of three acidleach, the three grades of same level of three acid leaching process acid leaching process.
After three grades of three acidleach finish, first open the 3rd surplus valve 3 that contains vanadium shale pickling equipment and discharge three grades of three pickling liquors, three grades of three pickling liquors are sent to the 4th liquid storage tank that contains vanadium shale pickling equipment or three grades of three pickling liquors through water pump 6; The 3rd three grades of three acid leaching residues that contain in vanadium shale pickling equipment are washed again, three grades of three acid leaching residues after washing are sent into Tailings Dam, three grades of wash waters after washing are sent to the 4th and contain vanadium shale pickling equipment or three grades of water washing tanks.
Fourth stage acidleach is to carry out four acidleach and once washing in the 4th contains vanadium shale pickling equipment
To contain vanadium shale calcining and three grades of pickling liquors are 1 by the solid-liquid mass ratio: mix in the 4th contains vanadium shale pickling equipment (1.5～2), then carry out an acidleach of level Four, and acid leaching process of level Four is with the one-level acid leaching process.
After an acidleach of level Four finishes, open the 4th surplus valve 3 that contains vanadium shale pickling equipment and discharge a pickling liquor of level Four, a pickling liquor of level Four is qualified pickling liquor, is sent to the liquid storage tank of a pickling liquor of level Four, is ready for use on the extraction operation.
Three grades of quadratic acid immersion liquid mix with the 4th acid leaching residue of level Four that contains in vanadium shale pickling equipment again, carry out the level Four secondary pickling, and level Four secondary pickling technique is with the one-level acid leaching process.
After the level Four secondary pickling finishes, open the 4th surplus valve 3 that contains vanadium shale pickling equipment and discharge the immersion liquid of level Four quadratic acid, it is standby that the liquid storage tank of level Four quadratic acid immersion liquid is sent in the immersion liquid of level Four quadratic acid.
Three grades of three pickling liquors mix with the 4th level Four secondary pickling slag that contains in vanadium shale pickling equipment, carry out three acidleach of level Four, the same level of three acid leaching process of level Four acid leaching process.
After three acidleach of level Four finish, open the 4th surplus valve 3 that contains vanadium shale pickling equipment and discharge three pickling liquors of level Four, it is standby that the liquid storage tank of three pickling liquors of level Four is sent in three pickling liquors of level Four.
Then contain three grades of wash waters in vanadium shale pickling equipment with addition of sulfuric acid to entering the 4th, mix with the 4th three acid leaching residues of level Four that contain in vanadium shale pickling equipment, carry out four acidleach of level Four, the same level of four acid leaching process of level Four acid leaching process.
After four acidleach of level Four finish, first open the 4th surplus valve 3 that contains vanadium shale pickling equipment and discharge four pickling liquors of level Four, four pickling liquors of level Four are standby through the liquid storage tank that water pump 6 is sent to four pickling liquors of level Four; The 4th four acid leaching residues of level Four that contain in vanadium shale pickling equipment are washed again, four acid leaching residues of level Four after washing are sent into Tailings Dam, it is standby that the level Four wash water after washing is sent to the level Four water washing tank.
The present embodiment described first contains vanadium shale pickling equipment, second and contains vanadium shale pickling equipment, the 3rd and contain the patent of invention technology that vanadium shale pickling equipment and the 4th contains " a kind of pickling equipment be used to containing vanadium shale " that vanadium shale pickling equipment applies on the same day for the applicant, and the concrete structure of this pickling equipment comprises cell body 4, upper cover plate 12, upflow tube 2, ore pulp circulation tube 11, liquid-inlet pipe 9 and drainage conduit 7.
The top of cell body 4 is hollow round table I, and the middle part is hollow cylinder I, and the bottom is hollow round table II, and the bottom is hollow cylinder II, and the diameter of the lower port diameter of hollow round table I and hollow cylinder I is identical with the back cut diameter of hollow round table II; The hollow round table I of cell body 4 is fixedly connected with upper cover plate 12 by bolt, and upper cover plate 12 is provided with opening for feed 1; The top of the hollow cylinder I of cell body 4 is connected with upflow tube 2 and ore pulp circulation tube 11, and upflow tube 2 is equipped with surplus valve 3 and water pump 6, liquid-inlet pipe or the external liquid storage tank of upflow tube 2 external subordinate pickling equipment.
The lower end of ore pulp circulation tube 11 communicates with the bottom of the hollow round table II of cell body 4, and ore pulp circulation tube 11 is equipped with sand pump 10; The hollow cylinder II of cell body 4 is provided with liquid-inlet pipe 9 and steam port 5, the upflow tube of the external higher level's pickling equipment of liquid-inlet pipe 9 or external storage acid pond, and the lower end of hollow cylinder II is provided with drainage conduit 7, and drainage conduit 7 is equipped with butterfly valve 8.
A kind of acidleach method that contains vanadium shale, be 3 and contain vanadium shale pickling equipment series connection use aspect equipment, the liquid-inlet pipe 9 that is each described pickling equipment is connected with the upflow tube 2 of its upper level pickling equipment, and the upflow tube 2 of each described pickling equipment is connected with the liquid-inlet pipe 9 of its next stage pickling equipment; Be three grades of three acidleach and once washing at process aspect, concrete grammar is as follows:
First step acidleach, except following parameter with the first step acidleach of embodiment 1.
To contain vanadium shale calcining and sulphuric acid soln is 1 by the solid-liquid mass ratio: mix in first contains vanadium shale pickling equipment (2～2.5), carry out again the one-level acidleach, the primary acids soaking technology is: be that 90～100 ℃ and sand pump 10 motor speeds are to stir 30～45min, standing 5～10min under the condition of 450～700r/min in temperature.
Second stage acidleach, except following parameter with the second stage acidleach of embodiment 1
To contain vanadium shale calcining and primary acids immersion liquid is 1 by the solid-liquid mass ratio: mix in second contains vanadium shale pickling equipment (2～2.5).
Third stage acidleach is to carry out three acidleach and once washing in the 3rd contains vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and secondary is 1 by the solid-liquid mass ratio: mix in the 3rd contains vanadium shale pickling equipment (2～2.5), then carry out three grades of acidleach, and three grades of acid leaching process are with the one-level acid leaching process.
After three grades of acidleach finish, open the 3rd surplus valve 3 that contains vanadium shale pickling equipment and discharge three grades of pickling liquors, three grades of pickling liquors are qualified pickling liquor, are sent to the liquid storage tank of three grades of pickling liquors, are ready for use on the extraction operation.
Three grades of acid leaching residues that secondary quadratic acid immersion liquid and the 3rd contains in vanadium shale pickling equipment mix, and carry out three grades of secondary picklings, and three grades of secondary pickling techniques are with the one-level acid leaching process.
After three grades of secondary picklings finish, open the 3rd surplus valve 3 that contains vanadium shale pickling equipment and discharge three grades of quadratic acid immersion liquid, the liquid storage tank that three grades of quadratic acid immersion liquid are sent in three grades of quadratic acid immersion liquid is standby.
Then contain secondary wash water in vanadium shale pickling equipment with addition of sulfuric acid to entering the 3rd, mix with the 3rd three grades of secondary pickling slags that contain in vanadium shale pickling equipment, carry out three grades of three acidleach, the three grades of same level of three acid leaching process acid leaching process.
After three grades of three acidleach finish, first open the 3rd surplus valve 3 that contains vanadium shale pickling equipment and discharge three grades of three pickling liquors, three grades of three pickling liquors are standby through the liquid storage tank that water pump 6 is sent to three grades of three pickling liquors; The 3rd three grades of three acid leaching residues that contain in vanadium shale pickling equipment are washed again, three grades of three acid leaching residues after washing are sent into Tailings Dam, it is standby that three grades of wash waters after washing are sent to three grades of water washing tanks.
The present embodiment described first contains vanadium shale pickling equipment, second and contains vanadium shale pickling equipment and the 3rd and contain vanadium shale pickling equipment all with embodiment 1.
A kind of acidleach method that contains vanadium shale.Be n and contain vanadium shale pickling equipment series connection use aspect equipment, namely the liquid-inlet pipe 9 of each described pickling equipment is connected with the upflow tube 2 of its upper level pickling equipment, and the upflow tube 2 of each described pickling equipment is connected with the liquid-inlet pipe 9 of its next stage pickling equipment; Be n acidleach of n level and once washing at process aspect, n is 5 or 6.Concrete grammar is as follows:
First step acidleach, except following parameter with the first step acidleach of embodiment 1.
To contain vanadium shale calcining and sulphuric acid soln is 1 by the solid-liquid mass ratio: mix in first contains vanadium shale pickling equipment (2.5～3), carry out again the one-level acidleach, the primary acids soaking technology is: be that 90～100 ℃ and sand pump 10 motor speeds are to stir 60～75min, standing 5～10min under the condition of 150～450r/min in temperature.
Second stage acidleach, except following parameter with the second stage acidleach of embodiment 1
To contain vanadium shale calcining and primary acids immersion liquid is 1 by the solid-liquid mass ratio: mix in second contains vanadium shale pickling equipment (2.5～3).
Third stage acidleach, except following parameter with the third stage acidleach of embodiment 1
To contain a pickling liquor of vanadium shale calcining and secondary is 1 by the solid-liquid mass ratio: mix in second contains vanadium shale pickling equipment (2.5～3).
……。
The acidleach of n level is to contain at n to carry out n acidleach and once washing in vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and n-1 level is 1 by the solid-liquid mass ratio: (2.5～3) contain in vanadium shale pickling equipment at n and mix, then carry out an acidleach of n level, and acid leaching process of n level is with the one-level acid leaching process.
After an acidleach of n level finishes, open the pickling liquor of surplus valve 3 discharge n levels that n contains vanadium shale pickling equipment, a pickling liquor of n level is qualified pickling liquor, is sent to the liquid storage tank of a pickling liquor of n level, is ready for use on the extraction operation.
The immersion liquid of n-1 level quadratic acid mixes with acid leaching residue of n level in n contains vanadium shale pickling equipment again, carries out n level secondary pickling, and n level secondary pickling technique is with the one-level acid leaching process.
After n level secondary pickling finishes, open the surplus valve 3 that n contains vanadium shale pickling equipment and discharge the immersion liquid of n level quadratic acid, it is standby that the liquid storage tank of n level quadratic acid immersion liquid is sent in the immersion liquid of n level quadratic acid.
……。
N-1 pickling liquor of n-1 level contains interior n-2 the acid leaching residue of n level of vanadium shale pickling equipment with n and mixes, and carries out n-1 acidleach of n level, the same level of n-1 acid leaching process of n level acid leaching process.
After n-1 acidleach of n level finishes, open the surplus valve 3 that n contains vanadium shale pickling equipment and discharge n-1 pickling liquor of n levels, it is standby that the liquid storage tank of n-1 pickling liquor of n level is sent in n-1 pickling liquor of n level.
Then contain n-1 level wash water in vanadium shale pickling equipment with addition of sulfuric acid to entering n, mix with n-1 acid leaching residue of n level in n contains vanadium shale pickling equipment, carry out n acidleach of n level, the same level of n acid leaching process of n level acid leaching process.
After n acidleach of n level finishes, first open n the pickling liquor of surplus valve 3 discharge n levels that n contains vanadium shale pickling equipment, n pickling liquor of n level is standby through the liquid storage tank that water pump 6 is sent to n pickling liquor of n level; N the acid leaching residue of n level that again n is contained in vanadium shale pickling equipment washed, and n the acid leaching residue of n level after washing sent into Tailings Dam, and it is standby that the n level wash water after washing is sent to n level water washing tank.
The present embodiment described first contain vanadium shale pickling equipment, second contain vanadium shale pickling equipment ... contain vanadium shale pickling equipment all with embodiment 1 with n.
This embodiment adopts the patent of invention technology of " a kind of pickling equipment be used to containing vanadium shale " that the applicant applies on the same day aspect equipment, n " a kind of pickling equipment be used to containing vanadium shale " series connection is used, be that each equipment liquid-inlet pipe 9 is connected with upper level equipment upflow tube 2, each equipment upflow tube 2 is connected with next stage equipment liquid-inlet pipe 9, has realized the continuous production of acid leaching process; Adopt n acidleach of n level and a water-washing technique at process aspect,, technological process is simple; Through n acidleach of n level with after once washing, the final pickling liquor of gained contains the requirement that vanadium concentration and pH value all satisfy follow-up extraction process, realize the recycle of sulphuric acid soln and other pickling liquor except qualified pickling liquor, reduced sour consumption, significantly reduced production cost; Contain vanadium shale pickling equipment by the mode that steam heating stirs, make the acidleach temperature reach 90～100 ℃, strengthened the chemical reaction of acid-leaching vanadium-extracted process, the vanadic acid rate of soaking reaches more than 88%.
Therefore, the characteristics that this embodiment has that simple, the sour consumption of technique is low, V leaching rate is high, follow-up extraction process requirement is satisfied in continuous production, pickling liquor.
Claims (5)
1. acidleach method that contains vanadium shale, it is characterized in that described acidleach method is: be n and contain vanadium shale pickling equipment series connection use aspect equipment, the liquid-inlet pipe (9) that is each described pickling equipment is connected with the upflow tube (2) of its upper level pickling equipment, and the upflow tube of each described pickling equipment (2) is connected with the liquid-inlet pipe (9) of its next stage pickling equipment; Be n acidleach of n level and once washing at process aspect, n is 3 ~ 6; Concrete grammar is as follows:
First step acidleach is to carry out an acidleach and once washing in first contains vanadium shale pickling equipment
First will contain vanadium shale calcining and sulphuric acid soln is 1:(1.5 ~ 3 by the solid-liquid mass ratio) mix in first contains vanadium shale pickling equipment, carry out again the one-level acidleach, the primary acids soaking technology is: be that 90 ~ 100 ℃ and sand pump (10) rotating speed are to stir 30 ~ 75min, standing 5 ~ 10min under the condition of 150 ~ 999r/min in temperature;
After the one-level acidleach finishes, first open the first surplus valve (3) that contains vanadium shale pickling equipment and discharge the primary acids immersion liquid, the primary acids immersion liquid is sent to the second liquid storing pool that contains vanadium shale pickling equipment or primary acids immersion liquid through water pump (6), again the first one-level acid leaching residue that contains in vanadium shale pickling equipment is washed, one-level acid leaching residue after washing is sent into Tailings Dam, and the one-level wash water after washing is sent to second and contains vanadium shale pickling equipment or one-level water washing tank;
Second stage acidleach is to carry out secondary pickling and once washing in second contains vanadium shale pickling equipment
To contain vanadium shale calcining and primary acids immersion liquid is 1:(1.5 ~ 3 by the solid-liquid mass ratio) mix in second contains vanadium shale pickling equipment, then carry out an acidleach of secondary, acid leaching process of secondary is with the one-level acid leaching process;
After an acidleach of secondary finishes, open the second surplus valve (3) that contains vanadium shale pickling equipment and discharge a pickling liquor of secondary, a pickling liquor of secondary is sent into the 3rd liquid storage tank that contains vanadium shale pickling equipment or a pickling liquor of secondary through water pump (6);
Then contain one-level wash water in vanadium shale pickling equipment with addition of sulfuric acid to entering second, mix with second acid leaching residue of secondary that contains in vanadium shale pickling equipment, carry out the secondary secondary pickling, secondary secondary pickling technique is with the one-level acid leaching process;
After the secondary secondary pickling finishes, first open the second surplus valve (3) that contains vanadium shale pickling equipment and discharge the immersion liquid of secondary quadratic acid, the immersion liquid of secondary quadratic acid is sent to the 3rd liquid storage tank that contains vanadium shale pickling equipment or the immersion liquid of secondary quadratic acid through water pump (6); The second secondary secondary pickling slag that contains in vanadium shale pickling equipment is washed again, the secondary secondary pickling slag after washing is sent into Tailings Dam, the secondary wash water after washing is sent to the 3rd and contains vanadium shale pickling equipment or secondary water washing tank;
Third stage acidleach is to carry out three acidleach and once washing in the 3rd contains vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and secondary is 1:(1.5 ~ 3 by the solid-liquid mass ratio) mix in the 3rd contains vanadium shale pickling equipment, then carry out three grades of acidleach, three grades of acid leaching process are with the one-level acid leaching process;
After three grades of acidleach finish, open the 3rd surplus valve (3) that contains vanadium shale pickling equipment and discharge three grades of pickling liquors, three grades of pickling liquors are sent into the 4th liquid storage tank that contains vanadium shale pickling equipment or three grades of pickling liquors through water pump (6);
Three grades of acid leaching residues that secondary quadratic acid immersion liquid and the 3rd contains in vanadium shale pickling equipment mix, and carry out three grades of secondary picklings, and three grades of secondary pickling techniques are with the one-level acid leaching process;
After three grades of secondary picklings finish, open the 3rd surplus valve (3) that contains vanadium shale pickling equipment and discharge three grades of quadratic acid immersion liquid, three grades of quadratic acid immersion liquid are sent into the 4th liquid storage tank that contains vanadium shale pickling equipment or three grades of quadratic acid immersion liquid through water pump (6);
Then contain secondary wash water in vanadium shale pickling equipment with addition of sulfuric acid to entering the 3rd, mix with the 3rd three grades of secondary pickling slags that contain in vanadium shale pickling equipment, carry out three grades of three acidleach, the three grades of same level of three acid leaching process acid leaching process;
After three grades of three acidleach finish, first open the 3rd surplus valve (3) that contains vanadium shale pickling equipment and discharge three grades of three pickling liquors, three grades of three pickling liquors are sent to the 4th liquid storage tank that contains vanadium shale pickling equipment or three grades of three pickling liquors through water pump (6); The 3rd three grades of three acid leaching residues that contain in vanadium shale pickling equipment are washed again, three grades of three acid leaching residues after washing are sent into Tailings Dam, three grades of wash waters after washing are sent to the 4th and contain vanadium shale pickling equipment or three grades of water washing tanks;
……；
The acidleach of n level is to contain at n to carry out n acidleach and once washing in vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and n-1 level is 1:(1.5 ~ 3 by the solid-liquid mass ratio) contain in vanadium shale pickling equipment at n and mix, then carry out an acidleach of n level, acid leaching process of n level is with the one-level acid leaching process;
After an acidleach of n level finishes, open the pickling liquor of surplus valve (3) discharge n level that n contains vanadium shale pickling equipment, a pickling liquor of n level is qualified pickling liquor, is sent to the liquid storage tank of a pickling liquor of n level, is ready for use on the extraction operation;
The immersion liquid of n-1 level quadratic acid mixes with acid leaching residue of n level in n contains vanadium shale pickling equipment again, carries out n level secondary pickling, and n level secondary pickling technique is with the one-level acid leaching process;
After n level secondary pickling finishes, open the surplus valve (3) that n contains vanadium shale pickling equipment and discharge the immersion liquid of n level quadratic acid, it is standby that the liquid storage tank of n level quadratic acid immersion liquid is sent in the immersion liquid of n level quadratic acid;
……；
N-1 pickling liquor of n-1 level contains interior n-2 the acid leaching residue of n level of vanadium shale pickling equipment with n and mixes, and carries out n-1 acidleach of n level, the same level of n-1 acid leaching process of n level acid leaching process;
After n-1 acidleach of n level finishes, open the surplus valve (3) that n contains vanadium shale pickling equipment and discharge n-1 pickling liquor of n level, it is standby that the liquid storage tank of n-1 pickling liquor of n level is sent in n-1 pickling liquor of n level;
Then contain n-1 level wash water in vanadium shale pickling equipment with addition of sulfuric acid to entering n, mix with n-1 acid leaching residue of n level in n contains vanadium shale pickling equipment, carry out n acidleach of n level, the same level of n acid leaching process of n level acid leaching process;
After n acidleach of n level finishes, first open n the pickling liquor of surplus valve (3) discharge n level that n contains vanadium shale pickling equipment, n pickling liquor of n level is standby through the liquid storage tank that water pump (6) is sent to n pickling liquor of n level; N the acid leaching residue of n level that again n is contained in vanadium shale pickling equipment washed, and n the acid leaching residue of n level after washing sent into Tailings Dam, and it is standby that the n level wash water after washing is sent to n level water washing tank.
2. the acidleach method that contains vanadium shale according to claim 1, is characterized in that the described vanadium shale calcining that contains is to contain vanadium shale raw ore prepared calcining after oxidizing roasting, contains the V of vanadium shale calcining
2O
5Grade is 0.6 ~ 1.2wt%.
3. the acidleach method that contains vanadium shale according to claim 1, the volumetric concentration that it is characterized in that described sulphuric acid soln is 15 ~ 35%.
4. the acidleach method that contains vanadium shale according to claim 1 is characterized in that describedly being 8 ~ 15% of the wash water volume that mixes with this sulfuric acid with addition of sulfuric acid with addition of amount.
5. the acidleach method that contains vanadium shale according to claim 1, it is characterized in that described first contain vanadium shale pickling equipment, second contain vanadium shale pickling equipment ... contain vanadium shale pickling equipment with n and be " a kind of pickling equipment be used to containing vanadium shale ", the concrete structure of this pickling equipment comprises cell body (4), upper cover plate (12), upflow tube (2), ore pulp circulation tube (11), liquid-inlet pipe (9) and drainage conduit (7);
The top of cell body (4) is the hollow round table I, and the middle part is the hollow cylinder I, and the bottom is the hollow round table II, and the bottom is the hollow cylinder II, and the diameter of the lower port diameter of hollow round table I and hollow cylinder I is identical with the back cut diameter of hollow round table II; The hollow round table I of cell body (4) is fixedly connected with upper cover plate (12) by bolt, and upper cover plate (12) is provided with opening for feed (1); The top of the hollow cylinder I of cell body (4) is connected with upflow tube (2) and ore pulp circulation tube (11), upflow tube (2) is equipped with surplus valve (3) and water pump (6), liquid-inlet pipe or the external liquid storage tank of upflow tube (2) external subordinate pickling equipment; The lower end of ore pulp circulation tube (11) communicates with the bottom of the hollow round table II of cell body (4), and ore pulp circulation tube (11) is equipped with sand pump (10); The hollow cylinder II of cell body (4) is provided with liquid-inlet pipe (9) and steam port (5), the sour pond of the upflow tube of the external higher level's pickling equipment of liquid-inlet pipe (9) or external storage, the lower end of hollow cylinder II is provided with drainage conduit (7), and drainage conduit (7) is equipped with butterfly valve (8).
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| CN2012100432538A CN102586595B (en) | 2012-02-24 | 2012-02-24 | Acid leaching method of vanadium-containing shale |
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| CN102586595B true CN102586595B (en) | 2013-05-08 |
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| CN104195342B (en) * | 2014-09-17 | 2016-06-01 | 华北电力大学 | A kind of method reclaiming Vanadium Pentoxide in FLAKES composition in waste and old SCR denitration |
| CN108069434B (en) * | 2016-11-14 | 2020-09-04 | 中国科学院过程工程研究所 | Method for extracting boron |
| CN112575204B (en) * | 2020-12-09 | 2022-08-09 | 四川卡森科技有限公司 | Lithium extraction method based on rotary kiln |
| CN115679126A (en) * | 2022-10-08 | 2023-02-03 | 武汉科技大学 | Vanadium shale step continuous leaching system |
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| CN101225480A (en) * | 2007-12-06 | 2008-07-23 | 昆明理工大学 | Combined vanadium leaching method for stone coal |
| CN101935768A (en) * | 2010-09-16 | 2011-01-05 | 中南大学 | Method for comprehensively recovering carbon from extraction of vanadium from stone coal |
| CN102002585A (en) * | 2010-11-15 | 2011-04-06 | 中南大学 | Method for producing vanadium iron with stone-like coal pickle liquor |
| CN102212708A (en) * | 2011-05-24 | 2011-10-12 | 湖南金大地材料股份有限公司 | Roasting-free wet vanadium extraction process for vanadium-containing mineral |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225480A (en) * | 2007-12-06 | 2008-07-23 | 昆明理工大学 | Combined vanadium leaching method for stone coal |
| CN101935768A (en) * | 2010-09-16 | 2011-01-05 | 中南大学 | Method for comprehensively recovering carbon from extraction of vanadium from stone coal |
| CN102002585A (en) * | 2010-11-15 | 2011-04-06 | 中南大学 | Method for producing vanadium iron with stone-like coal pickle liquor |
| CN102212708A (en) * | 2011-05-24 | 2011-10-12 | 湖南金大地材料股份有限公司 | Roasting-free wet vanadium extraction process for vanadium-containing mineral |
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