CN102586595A - Acid leaching method of vanadium-containing shale - Google Patents
Acid leaching method of vanadium-containing shale Download PDFInfo
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- CN102586595A CN102586595A CN2012100432538A CN201210043253A CN102586595A CN 102586595 A CN102586595 A CN 102586595A CN 2012100432538 A CN2012100432538 A CN 2012100432538A CN 201210043253 A CN201210043253 A CN 201210043253A CN 102586595 A CN102586595 A CN 102586595A
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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 the vanadium shale process for extracting vanadium flow process, leaching is indispensable operation, will contain in the solution such as vanadium in the 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 the 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 big, vanadic acid soaks that rate is low, defectives such as subsequent technique requirement can not be directly satisfied in pickling liquor.
Secondary acid leaching process (Lu Zhaoling; From bone coal, extract the experimental study and the industrial practice of Vanadium Pentoxide in FLAKES 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): 1～4) have 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 defective such as 80%.
Multistage acid leaching process, a kind of is heap leaching method, and the shortcoming of this technology is that working cycle is long, and floor space is big, and environmental problem is serious; Another kind is the multi-stage countercurrent stirring technique like " from contain navajoite stone, reclaiming the method for vanadium " (US No4666512) patented technology, " coarse-grained method in a kind of segmentation formic acid circulation acidleach red soil nickel ore " (CN200810072530.1) patented technology, " 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 technology exists the acidleach process not carry out continuously; Pickling equipment needs to be used to realize the process of solid-liquid separation and transportation pickling liquor and acid leaching residue with worm conveyor and lift; Complex process; Working cycle is long, and corresponding utility appliance is shortcoming such as acid-alkali-corrosive-resisting not.
Summary of the invention
The present invention is intended to overcome the deficiency of prior art, but purpose provides that simple, the sour consumption of a kind of technology is low, vanadic acid soaks rate height continuous production and the acidleach fluid power satisfies the acidleach method that contains vanadium shale of subsequent technique requirement.
For realizing above-mentioned purpose; 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 said pickling equipment is connected with the upflow tube of its upper level pickling equipment, and the upflow tube of each said pickling equipment is connected with the liquid-inlet pipe of its next stage pickling equipment; At process aspect is n acidleach of n level and once washing, and n is 3～6.Concrete grammar is following:
First step acidleach is to contain first to carry out an acidleach and once washing in the vanadium shale pickling equipment
To contain vanadium shale calcining and sulphuric acid soln earlier is 1 by the solid-liquid mass ratio: (1.5～3) contain in the vanadium shale pickling equipment first and mix; Carry out the one-level acidleach again; The primary acids soaking technology is: being 90～100 ℃ in temperature is to stir 30～75min under the condition of 150～999r/min with the sand pump rotating speed, leaves standstill 5～10min.
After the one-level acidleach finishes; Unlatching first earlier contains the surplus valve of vanadium shale pickling equipment and discharges the primary acids immersion liquid; The primary acids immersion liquid through water pump be sent to second contain vanadium shale pickling equipment or primary acids immersion liquid liquid storing pool; The first one-level acid leaching residue that contain in the vanadium shale pickling equipment is washed again, the one-level acid leaching residue after the washing is sent into the mine tailing storehouse, the one-level wash water after the washing is sent to second and contains vanadium shale pickling equipment or one-level water washing tank.
Second stage acidleach is to contain second to carry out secondary pickling and once washing in the vanadium shale pickling equipment
To contain vanadium shale calcining and primary acids immersion liquid is 1 by the solid-liquid mass ratio: (1.5～3) contain in the vanadium shale pickling equipment second and mix, and carry out an acidleach of secondary again, and acid leaching process of secondary is with the one-level acid leaching process;
After an acidleach of secondary finishes, open second contain vanadium shale pickling equipment surplus valve discharge a pickling liquor of secondary, a pickling liquor of secondary through water pump send into the 3rd contain a vanadium shale pickling equipment or a pickling liquor of secondary liquid storage tank;
Contain one-level wash water in the vanadium shale pickling equipment with addition of sulfuric acid to getting into second then, mix with second acid leaching residue of secondary of containing in the vanadium shale pickling equipment, carry out the secondary secondary pickling, secondary secondary pickling technology is with the one-level acid leaching process;
After the secondary secondary pickling finishes, open earlier second contain vanadium shale pickling equipment surplus valve discharge the immersion liquid of secondary quadratic acid, the immersion liquid of secondary quadratic acid through water pump be sent to the 3rd contain vanadium shale pickling equipment or the immersion liquid of secondary quadratic acid liquid storage tank; The second secondary secondary pickling slag that contain in the vanadium shale pickling equipment is washed again, the secondary secondary pickling slag after the washing is sent into the mine tailing storehouse, the secondary wash water after the washing is sent to the 3rd and contains vanadium shale pickling equipment or secondary water washing tank;
Third stage acidleach is to contain the 3rd to carry out three acidleach and once washing in the vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and secondary is 1 by the solid-liquid mass ratio: (1.5～3) contain in the vanadium shale pickling equipment the 3rd and mix, and carry out three grades of acidleach again, and three grades of acid leaching process are with the one-level acid leaching process;
After three grades of acidleach finish, open the 3rd contain vanadium shale pickling equipment surplus valve discharge three grades of pickling liquors, three grades of pickling liquors through water pump send into the 4th contain vanadium shale pickling equipment or three grades of pickling liquors liquid storage tank;
Three grades of acid leaching residues that secondary quadratic acid immersion liquid and the 3rd contains in the vanadium shale pickling equipment mix, and carry out three grades of secondary picklings, and three grades of secondary pickling technologies are with the one-level acid leaching process;
After three grades of secondary picklings finish, open the 3rd contain vanadium shale pickling equipment surplus valve discharge three grades of quadratic acid immersion liquid, three grades of quadratic acid immersion liquid through water pump send into the 4th contain vanadium shale pickling equipment or three grades of quadratic acid immersion liquid liquid storage tank;
Contain secondary wash water in the vanadium shale pickling equipment with addition of sulfuric acid to getting into the 3rd then, mixes, carry out three grades of three acidleach, same grade of acid leaching process of three grades of three acid leaching process with the 3rd three grades of secondary pickling slags containing in the vanadium shale pickling equipment;
After three grades of three acidleach finish, open earlier the 3rd contain vanadium shale pickling equipment surplus valve discharge three grades of three pickling liquors, three grades of three pickling liquors through water pump be sent to the 4th contain vanadium shale pickling equipment or three grades of three pickling liquors liquid storage tank; The 3rd three grades of three acid leaching residues containing in the vanadium shale pickling equipment are washed again, three grades of three acid leaching residues after the washing are sent into the mine tailing storehouse, three grades of wash waters after the 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 the 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 the vanadium shale pickling equipment at n and mix, and carry out an acidleach of n level again, 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 technology 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 subsequent use 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 subsequent use that the liquid storage tank of n-1 pickling liquor of n level is sent in n-1 pickling liquor of n level;
Contain n-1 level wash water in the vanadium shale pickling equipment with addition of sulfuric acid to getting into n then, mix, carry out n acidleach of n level, same grade of acid leaching process of n acid leaching process of n level with n-1 acid leaching residue of n level in n contains vanadium shale pickling equipment;
After n acidleach of n level finishes, open n the pickling liquor of surplus valve discharge n level that n contains vanadium shale pickling equipment earlier, n pickling liquor of n level is subsequent use 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 the vanadium shale pickling equipment washed, and n the acid leaching residue of n level after the washing sent into the mine tailing storehouse, and it is subsequent use that the n level wash water after the washing is sent to n level water washing tank.
In technique scheme: the said 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 said sulphuric acid soln is 15～35%; Said with addition of vitriolic with addition of the amount for and 8～15% of this sulfuric acid institute blended wash water volume.
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 that is used to contain 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 platform I, and the middle part is hollow cylinder I, and the bottom is hollow round platform II, and the bottom is hollow cylinder II, and the diameter of the lower port diameter of hollow round platform I and hollow cylinder I is identical with the back cut diameter of hollow round platform II; The hollow round platform I of cell body is fixedly connected with upper cover plate through 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, the liquid-inlet pipe or the external liquid storage tank of the external subordinate of upflow tube pickling equipment.
The lower end of ore pulp circulation tube communicates with the bottom of the hollow round platform 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 adopt technique scheme; The present invention adopts the patent of invention technology of " a kind of pickling equipment that is used to contain vanadium shale " that the applicant applies on the same day aspect equipment; N " a kind of pickling equipment that is used to contain 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 that qualified pickling liquor, reduced sour consumption, significantly reduced production cost; Contain vanadium shale pickling equipment through 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 technology is low, vanadium leaching yield height, continuous production, pickling liquor satisfy follow-up extraction process requirement.
Description of drawings
Fig. 1 is a kind of process flow sheet of the present invention.
Fig. 2 is a kind of equipment synoptic diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention being done further description, 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%; With addition of vitriolic be and 8～15% of this sulfuric acid institute blended wash water volume with addition of amount.Repeat no more in the 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 said pickling equipment is connected with the upflow tube 2 of its upper level pickling equipment, and the upflow tube 2 of each said pickling equipment is connected with the liquid-inlet pipe 9 of its next stage pickling equipment; At process aspect is four acidleach of level Four and once washing, concrete grammar such as as shown in Figure 1:
First step acidleach is to contain first to carry out an acidleach and once washing in the vanadium shale pickling equipment
To contain vanadium shale calcining and sulphuric acid soln earlier is 1 by the solid-liquid mass ratio: (1.5～2) contain in the vanadium shale pickling equipment first and mix; Carry out the one-level acidleach again; The primary acids soaking technology is: being 90～100 ℃ in temperature is to stir 45～60min under the condition of 700～999r/min with sand pump 10 rotating speeds, leaves standstill 5～10min.
After the one-level acidleach finishes; Unlatching first earlier contains the surplus valve 3 of vanadium shale pickling equipment and discharges the primary acids immersion liquid; The primary acids immersion liquid through water pump 6 be sent to second contain vanadium shale pickling equipment or primary acids immersion liquid liquid storing pool; The first one-level acid leaching residue that contain in the vanadium shale pickling equipment is washed again, the one-level acid leaching residue after the washing is sent into the mine tailing storehouse, the one-level wash water after the washing is sent to second and contains vanadium shale pickling equipment or one-level water washing tank.
Second stage acidleach is to contain second to carry out secondary pickling and once washing in the vanadium shale pickling equipment
To contain vanadium shale calcining and primary acids immersion liquid is 1 by the solid-liquid mass ratio: (1.5～2) contain in the vanadium shale pickling equipment second and mix, and carry out an acidleach of secondary again, and acid leaching process of secondary is with the one-level acid leaching process.
After an acidleach of secondary finishes, open second contain vanadium shale pickling equipment surplus valve 3 discharge a pickling liquor of secondarys, a pickling liquor of secondary through water pump 6 send into the 3rd contain a vanadium shale pickling equipment or a pickling liquor of secondary liquid storage tank.
Contain one-level wash water in the vanadium shale pickling equipment with addition of sulfuric acid to getting into second then, mix with second acid leaching residue of secondary of containing in the vanadium shale pickling equipment, carry out the secondary secondary pickling, secondary secondary pickling technology is with the one-level acid leaching process.
After the secondary secondary pickling finishes, open earlier second contain vanadium shale pickling equipment surplus valve 3 discharge the immersion liquid of secondary quadratic acid, the immersion liquid of secondary quadratic acid through water pump 6 be sent to the 3rd contain vanadium shale pickling equipment or the immersion liquid of secondary quadratic acid liquid storage tank; The second secondary secondary pickling slag that contain in the vanadium shale pickling equipment is washed again, the secondary secondary pickling slag after the washing is sent into the mine tailing storehouse, the secondary wash water after the washing is sent to the 3rd and contains vanadium shale pickling equipment or secondary water washing tank.
Third stage acidleach is to contain the 3rd to carry out three acidleach and once washing in the vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and secondary is 1 by the solid-liquid mass ratio: (1.5～2) contain in the vanadium shale pickling equipment the 3rd and mix, and carry out three grades of acidleach again, and three grades of acid leaching process are with the one-level acid leaching process.
After three grades of acidleach finish, open the 3rd contain vanadium shale pickling equipment surplus valve 3 discharge three grades of pickling liquors, three grades of pickling liquors through water pump 6 send into the 4th contain vanadium shale pickling equipment or three grades of pickling liquors liquid storage tank.
Three grades of acid leaching residues that secondary quadratic acid immersion liquid and the 3rd contains in the vanadium shale pickling equipment mix, and carry out three grades of secondary picklings, and three grades of secondary pickling technologies are with the one-level acid leaching process.
After three grades of secondary picklings finish, open the 3rd contain vanadium shale pickling equipment surplus valve 3 discharge three grades of quadratic acid immersion liquid, three grades of quadratic acid immersion liquid through water pump 6 send into the 4th contain vanadium shale pickling equipment or three grades of quadratic acid immersion liquid liquid storage tank.
Contain secondary wash water in the vanadium shale pickling equipment with addition of sulfuric acid to getting into the 3rd then, mixes, carry out three grades of three acidleach, same grade of acid leaching process of three grades of three acid leaching process with the 3rd three grades of secondary pickling slags containing in the vanadium shale pickling equipment.
After three grades of three acidleach finish, open earlier the 3rd contain vanadium shale pickling equipment surplus valve 3 discharge three grades of three pickling liquors, three grades of three pickling liquors through water pump 6 be sent to the 4th contain vanadium shale pickling equipment or three grades of three pickling liquors liquid storage tank; The 3rd three grades of three acid leaching residues containing in the vanadium shale pickling equipment are washed again, three grades of three acid leaching residues after the washing are sent into the mine tailing storehouse, three grades of wash waters after the washing are sent to the 4th and contain vanadium shale pickling equipment or three grades of water washing tanks.
Fourth stage acidleach is to contain the 4th to carry out four acidleach and once washing in the vanadium shale pickling equipment
To contain vanadium shale calcining and three grades of pickling liquors are 1 by the solid-liquid mass ratio: (1.5～2) contain in the vanadium shale pickling equipment the 4th and mix, and carry out an acidleach of level Four again, 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 contain vanadium shale pickling equipment surplus valve 3 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 of containing in the vanadium shale pickling equipment again, carry out the level Four secondary pickling, and level Four secondary pickling technology is with the one-level acid leaching process.
After the level Four secondary pickling finishes, open the 4th contain vanadium shale pickling equipment surplus valve 3 discharge the immersion liquid of level Four quadratic acid, it is subsequent use that the liquid storage tank of level Four quadratic acid immersion liquid is sent in the immersion liquid of level Four quadratic acid.
The level Four secondary pickling slag that three grades of three pickling liquors and the 4th contain in the vanadium shale pickling equipment mixes, carries out three acidleach of level Four, same grade of acid leaching process of three acid leaching process of level Four.
After three acidleach of level Four finish, open the 4th contain vanadium shale pickling equipment surplus valve 3 discharge three pickling liquors of level Four, it is subsequent use that the liquid storage tank of three pickling liquors of level Four is sent in three pickling liquors of level Four.
Contain three grades of wash waters in the vanadium shale pickling equipment with addition of sulfuric acid to getting into the 4th then, mixes, carry out four acidleach of level Four, same grade of acid leaching process of four acid leaching process of level Four with the 4th three acid leaching residues of level Four of containing in the vanadium shale pickling equipment.
After four acidleach of level Four finished, unlatching the 4th earlier contained the surplus valve 3 of vanadium shale pickling equipment and discharges four pickling liquors of level Four, and four pickling liquors of level Four are subsequent use 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 of containing in the vanadium shale pickling equipment are washed again, four acid leaching residues of level Four after the washing are sent into the mine tailing storehouse, it is subsequent use that the level Four wash water after the washing is sent to the level Four water washing tank.
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 that is used to contain vanadium shale " that vanadium shale pickling equipment applies for for the applicant on the same day, 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 platform I, and the middle part is hollow cylinder I, and the bottom is hollow round platform II, and the bottom is hollow cylinder II, and the diameter of the lower port diameter of hollow round platform I and hollow cylinder I is identical with the back cut diameter of hollow round platform II; The hollow round platform I of cell body 4 is fixedly connected with upper cover plate 12 through 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, the liquid-inlet pipe or the external liquid storage tank of upflow tube 2 external subordinate pickling equipments.
The lower end of ore pulp circulation tube 11 communicates with the bottom of the hollow round platform 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 liquid-inlet pipe 9 external higher level's pickling equipments 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 said pickling equipment is connected with the upflow tube 2 of its upper level pickling equipment, and the upflow tube 2 of each said pickling equipment is connected with the liquid-inlet pipe 9 of its next stage pickling equipment; At process aspect is three grades of three acidleach and once washing, and concrete grammar is following:
First step acidleach, except that 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: (2～2.5) contain in the vanadium shale pickling equipment first and mix; Carry out the one-level acidleach again; The primary acids soaking technology is: being 90～100 ℃ in temperature is to stir 30～45min under the condition of 450～700r/min with sand pump 10 motor speeds, leaves standstill 5～10min.
Second stage acidleach, except that 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: (2～2.5) contain in the vanadium shale pickling equipment second and mix.
Third stage acidleach is to contain the 3rd to carry out three acidleach and once washing in the vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and secondary is 1 by the solid-liquid mass ratio: (2～2.5) contain in the vanadium shale pickling equipment the 3rd and mix, and carry out three grades of acidleach again, and three grades of acid leaching process are with the one-level acid leaching process.
After three grades of acidleach finish, open the 3rd contain vanadium shale pickling equipment surplus valve 3 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 the vanadium shale pickling equipment mix, and carry out three grades of secondary picklings, and three grades of secondary pickling technologies are with the one-level acid leaching process.
After three grades of secondary picklings finish, open the 3rd contain vanadium shale pickling equipment surplus valve 3 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 subsequent use.
Contain secondary wash water in the vanadium shale pickling equipment with addition of sulfuric acid to getting into the 3rd then, mixes, carry out three grades of three acidleach, same grade of acid leaching process of three grades of three acid leaching process with the 3rd three grades of secondary pickling slags containing in the vanadium shale pickling equipment.
After three grades of three acidleach finished, unlatching the 3rd earlier contained the surplus valve 3 of vanadium shale pickling equipment and discharges three grades of three pickling liquors, and three grades of three pickling liquors are subsequent use 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 containing in the vanadium shale pickling equipment are washed again, three grades of three acid leaching residues after the washing are sent into the mine tailing storehouse, it is subsequent use that three grades of wash waters after the washing are sent to three grades of water washing tanks.
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, promptly the liquid-inlet pipe 9 of each said pickling equipment is connected with the upflow tube 2 of its upper level pickling equipment, and the upflow tube 2 of each said pickling equipment is connected with the liquid-inlet pipe 9 of its next stage pickling equipment; At process aspect is n acidleach of n level and once washing, and n is 5 or 6.Concrete grammar is following:
First step acidleach, except that 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: (2.5～3) contain in the vanadium shale pickling equipment first and mix; Carry out the one-level acidleach again; The primary acids soaking technology is: being 90～100 ℃ in temperature is to stir 60～75min under the condition of 150～450r/min with sand pump 10 motor speeds, leaves standstill 5～10min.
Second stage acidleach, except that 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: (2.5～3) contain in the vanadium shale pickling equipment second and mix.
Third stage acidleach, except that 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: (2.5～3) contain in the vanadium shale pickling equipment second and mix.
……。
The acidleach of n level is to contain at n to carry out n acidleach and once washing in the 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 the vanadium shale pickling equipment at n and mix, and carry out an acidleach of n level again, 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 technology 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 subsequent use 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 subsequent use that the liquid storage tank of n-1 pickling liquor of n level is sent in n-1 pickling liquor of n level.
Contain n-1 level wash water in the vanadium shale pickling equipment with addition of sulfuric acid to getting into n then, mix, carry out n acidleach of n level, same grade of acid leaching process of n acid leaching process of n level with n-1 acid leaching residue of n level in n contains vanadium shale pickling equipment.
After n acidleach of n level finishes, open n the pickling liquor of surplus valve 3 discharge n levels that n contains vanadium shale pickling equipment earlier, n pickling liquor of n level is subsequent use 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 the vanadium shale pickling equipment washed, and n the acid leaching residue of n level after the washing sent into the mine tailing storehouse, and it is subsequent use that the n level wash water after the washing is sent to n level water washing tank.
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 that is used to contain vanadium shale " that the applicant applies on the same day aspect equipment; N " a kind of pickling equipment that is used to contain 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 that qualified pickling liquor, reduced sour consumption, significantly reduced production cost; Contain vanadium shale pickling equipment through 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 technology is low, vanadium leaching yield height, continuous production, pickling liquor satisfy follow-up extraction process requirement.
Claims (5)
1. acidleach method that contains vanadium shale.It is characterized in that said acidleach method is: be n and contain vanadium shale pickling equipment series connection use aspect equipment; The liquid-inlet pipe (9) that is each said pickling equipment is connected with the upflow tube (2) of its upper level pickling equipment, and the upflow tube of each said pickling equipment (2) is connected with the liquid-inlet pipe (9) of its next stage pickling equipment; At process aspect is n acidleach of n level and once washing, and n is 3～6; Concrete grammar is following:
First step acidleach is to contain first to carry out an acidleach and once washing in the vanadium shale pickling equipment
To contain vanadium shale calcining and sulphuric acid soln earlier is 1 by the solid-liquid mass ratio: (1.5～3) contain in the vanadium shale pickling equipment first and mix; Carry out the one-level acidleach again; The primary acids soaking technology is: in temperature is that 90～100 ℃ and sand pump (10) rotating speed are to stir 30～75min under the condition of 150～999r/min, leaves standstill 5～10min;
After the one-level acidleach finishes; Unlatching first earlier contains the surplus valve (3) of vanadium shale pickling equipment and discharges the primary acids immersion liquid; The primary acids immersion liquid through water pump (6) be sent to second contain vanadium shale pickling equipment or primary acids immersion liquid liquid storing pool; The first one-level acid leaching residue that contain in the vanadium shale pickling equipment is washed again, the one-level acid leaching residue after the washing is sent into the mine tailing storehouse, the one-level wash water after the washing is sent to second and contains vanadium shale pickling equipment or one-level water washing tank;
Second stage acidleach is to contain second to carry out secondary pickling and once washing in the vanadium shale pickling equipment
To contain vanadium shale calcining and primary acids immersion liquid is 1 by the solid-liquid mass ratio: (1.5～3) contain in the vanadium shale pickling equipment second and mix, and carry out an acidleach of secondary again, and acid leaching process of secondary is with the one-level acid leaching process;
After an acidleach of secondary finishes, open second contain vanadium shale pickling equipment surplus valve (3) discharge a pickling liquor of secondary, a pickling liquor of secondary through water pump (6) send into the 3rd contain a vanadium shale pickling equipment or a pickling liquor of secondary liquid storage tank;
Contain one-level wash water in the vanadium shale pickling equipment with addition of sulfuric acid to getting into second then, mix with second acid leaching residue of secondary of containing in the vanadium shale pickling equipment, carry out the secondary secondary pickling, secondary secondary pickling technology is with the one-level acid leaching process;
After the secondary secondary pickling finishes, open earlier second contain vanadium shale pickling equipment surplus valve (3) discharge the immersion liquid of secondary quadratic acid, the immersion liquid of secondary quadratic acid through water pump (6) be sent to the 3rd contain vanadium shale pickling equipment or the immersion liquid of secondary quadratic acid liquid storage tank; The second secondary secondary pickling slag that contain in the vanadium shale pickling equipment is washed again, the secondary secondary pickling slag after the washing is sent into the mine tailing storehouse, the secondary wash water after the washing is sent to the 3rd and contains vanadium shale pickling equipment or secondary water washing tank;
Third stage acidleach is to contain the 3rd to carry out three acidleach and once washing in the vanadium shale pickling equipment
To contain a pickling liquor of vanadium shale calcining and secondary is 1 by the solid-liquid mass ratio: (1.5～3) contain in the vanadium shale pickling equipment the 3rd and mix, and carry out three grades of acidleach again, and three grades of acid leaching process are with the one-level acid leaching process;
After three grades of acidleach finish, open the 3rd contain vanadium shale pickling equipment surplus valve (3) discharge three grades of pickling liquors, three grades of pickling liquors through water pump (6) send into the 4th contain vanadium shale pickling equipment or three grades of pickling liquors liquid storage tank;
Three grades of acid leaching residues that secondary quadratic acid immersion liquid and the 3rd contains in the vanadium shale pickling equipment mix, and carry out three grades of secondary picklings, and three grades of secondary pickling technologies are with the one-level acid leaching process;
After three grades of secondary picklings finish, open the 3rd contain vanadium shale pickling equipment surplus valve (3) discharge three grades of quadratic acid immersion liquid, three grades of quadratic acid immersion liquid through water pump (6) send into the 4th contain vanadium shale pickling equipment or three grades of quadratic acid immersion liquid liquid storage tank;
Contain secondary wash water in the vanadium shale pickling equipment with addition of sulfuric acid to getting into the 3rd then, mixes, carry out three grades of three acidleach, same grade of acid leaching process of three grades of three acid leaching process with the 3rd three grades of secondary pickling slags containing in the vanadium shale pickling equipment;
After three grades of three acidleach finish, open earlier the 3rd contain vanadium shale pickling equipment surplus valve (3) discharge three grades of three pickling liquors, three grades of three pickling liquors through water pump (6) be sent to the 4th contain vanadium shale pickling equipment or three grades of three pickling liquors liquid storage tank; The 3rd three grades of three acid leaching residues containing in the vanadium shale pickling equipment are washed again, three grades of three acid leaching residues after the washing are sent into the mine tailing storehouse, three grades of wash waters after the 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 the 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 the vanadium shale pickling equipment at n and mix, and carry out an acidleach of n level again, 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 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 technology 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 subsequent use 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 subsequent use that the liquid storage tank of n-1 pickling liquor of n level is sent in n-1 pickling liquor of n level;
Contain n-1 level wash water in the vanadium shale pickling equipment with addition of sulfuric acid to getting into n then, mix, carry out n acidleach of n level, same grade of acid leaching process of n acid leaching process of n level with n-1 acid leaching residue of n level in n contains vanadium shale pickling equipment;
After n acidleach of n level finishes, open n the pickling liquor of surplus valve (3) discharge n level that n contains vanadium shale pickling equipment earlier, n pickling liquor of n level is subsequent use 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 the vanadium shale pickling equipment washed, and n the acid leaching residue of n level after the washing sent into the mine tailing storehouse, and it is subsequent use that the n level wash water after the 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 said 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 said sulphuric acid soln is 15～35%.
4. the acidleach method that contains vanadium shale according to claim 1, it is characterized in that said with addition of vitriolic with addition of the amount for and 8～15% of this sulfuric acid institute blended wash water volume.
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 that is used to contain 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 hollow round platform I, and the middle part is hollow cylinder I, and the bottom is hollow round platform II, and the bottom is hollow cylinder II, and the diameter of the lower port diameter of hollow round platform I and hollow cylinder I is identical with the back cut diameter of hollow round platform II; The hollow round platform I of cell body (4) is fixedly connected with upper cover plate (12) through 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), the liquid-inlet pipe or the external liquid storage tank of the external subordinate of upflow tube (2) pickling equipment; The lower end of ore pulp circulation tube (11) communicates with the bottom of the hollow round platform 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).
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| CN104195342A (en) * | 2014-09-17 | 2014-12-10 | 华北电力大学 | Method for recycling vanadium pentoxide in waste SCR (Selective Catalytic Reduction) denitration catalyst |
| CN108070717A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院过程工程研究所 | The adverse current tandem for controlling liquid-solid ratio simultaneously and embathing completion liquid concentration embathes method and system |
| CN112575204A (en) * | 2020-12-09 | 2021-03-30 | 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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| 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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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104195342A (en) * | 2014-09-17 | 2014-12-10 | 华北电力大学 | Method for recycling vanadium pentoxide in waste SCR (Selective Catalytic Reduction) denitration catalyst |
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| CN108070717A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院过程工程研究所 | The adverse current tandem for controlling liquid-solid ratio simultaneously and embathing completion liquid concentration embathes method and system |
| CN112575204A (en) * | 2020-12-09 | 2021-03-30 | 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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| CN102586595B (en) | 2013-05-08 |
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