CN203474876U - Ionic rare-earth mine extraction device based on membrane technology - Google Patents
Ionic rare-earth mine extraction device based on membrane technology Download PDFInfo
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- CN203474876U CN203474876U CN201320475601.9U CN201320475601U CN203474876U CN 203474876 U CN203474876 U CN 203474876U CN 201320475601 U CN201320475601 U CN 201320475601U CN 203474876 U CN203474876 U CN 203474876U
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Abstract
The utility model relates to an ionic rare-earth mine extraction process based on a membrane integration technology. The process mainly comprises the following steps: removing impurities in a rare-earth mineral impregnation solution, and performing solid-liquid separation on the impregnation solution after impurity removal by adopting a ceramic membrane to remove suspended matters in the impregnation solution, and slagging a ceramic membrane concentrated solution after being treated by adopting a plate-and-frame filter press; extracting and separating single rare-earth element by adopting an extraction process when the rare-earth impregnation solution is subjected to nanofiltration concentration and reaches the concentration being 60-70g/L, and directly returning a nanofiltration clear solution in the impregnation process as the nanofiltration clear solution contains rich leaching agents. According to the ionic rare-earth mine extraction process, the impurity removal, the separation and the concentrated enrichment are performed on the rare-earth mineral impregnation solution by utilizing the membrane separation integration technology, so that rare-earth ions in the impregnation solution can be purified and concentrated, and the extraction in the next process can be facilitated; the impregnation solution separated from rare-earth can be directly returned to the impregnation process due to the low concentration of the rare-earth ions and the high concentration of the impregnation solution. Therefore, the recycling rate of the rare-earth ions can be greatly improved, the discharge capacity of impregnation waste water can be reduced, and the ionic rare-earth mine extraction process has remarkable environmental benefits and economic benefits.
Description
Technical field
The utility model relates to a kind of ion type rareearth ore rare earth extraction process based on membrane technique, relate in particular to a kind of employing removal of impurities, ceramic membrane separation, nanofiltration membrane concentration ion type rareearth ore maceration liquid, so that maceration liquid reaches the operation requirement of direct extraction after processing, belong to rare-earth mineral and extract separation field.
Background technology
Take Jiangxi, Guangdong, Hunan, Fujian, be that main south has abundant ion adsorption type re and (is called for short ion type rareearth, or title weathered superficial leaching rare-earth) resource, its principal feature is: (1) grade is low, generally below 3/1000ths, most ten thousand/several; (2) partition of rare earth element is complete, and especially middle heavy rare earths content is high, thereby obtains extensive attention both domestic and external; (3) radioactive element content is low, and majority belongs to on-radiation mineral deposit; (4) existence form is unique, and mainly the form with ionic state is adsorbed in clay mineral surface.
The technological process of traditional ion type rareearth ore Extraction of rare eart mainly comprises with ionogen soaks ore deposit agent leaching rare earth, leaches feed liquid pre-treatment removal of impurities (or extracting and enriching), with the precipitating rare earths such as oxalic acid or bicarbonate of ammonia, drying or calcination, obtains can be used for the concentrate such as the rare earth oxide of follow-up extracting and separating or carbonated rare earth.Through the extracting and separating of separation plant, can produce the single rare earth product of various purity and specification again.But adopt the chemical constitution of ionogen leaching gained rare earth maceration liquid complicated, the low and foreign matter content high of rare earth concentration, has affected the purify process of follow-up rare earth to a certain extent.And along with rare-earth mineral is exploited more and more lean ore, if cannot produce qualified rare-earth products from the rare earth resources of lean ore more and more, just cannot bring into play well the resources advantage of China's Rare-earth Industry.Although " ore deposit novel process is soaked in original place " solved the dilution problem of rare-earth mineral, the phenomenon that consequent maceration liquid middle-weight rare earths concentration is low, impurity is high does not still solve.It is reported, the rare earth ion concentration of existing ion type rareearth ore maceration liquid drops to 0.1 ~ 0.2g/L by the 2g/L in past, and is rich in the impurity such as aluminium, iron of high density.The maceration liquid of lower concentration like this, not only greatly increased the volume of the required maceration liquid of Extraction of rare earth, improved the extraction cost of unit rare earth, and so complicated and tediously long technical process especially carbon ammonium precipitation technique also increased the loss amount of rare earth, increased sewage quantity and the concentration of environmental protection treatment simultaneously.Therefore, be necessary further to improve the Technology of Extraction of rare earth in ion type rareearth ore maceration liquid.
Membrane sepn is that to take outside energy or chemical potential difference be impellent, and two-pack or multi-component Solute and solvent are separated from each other by film, and and then a kind of method of purification and enrichment.It can carry out the separation of solid-liquid, colloid, can carry out the separation between molecule, ion again, thereby can meet effective constituent separation and enrichment in rare-earth trade.The aperture screening mechanism of membrane sepn and effectively ion selectivity have determined the high and good separating effect of the precision of membrane sepn.Membrane process does not produce phase transformation and easy amplification simple to operate, so its running cost is low and can serialization automated operation and scale operation.The high strength of this adventitia and chemical stability have determined that it is suitable for use in harsh environmental system.
Because membrane separation technique has the unrivaled advantage of traditional separation method, metallurgy separation scientific and engineering institute of Central South University proposes application of membrane separation technology in improving existing Rare Earth Separation technique, make it mutually integrated with extraction process, and applied for patent CN02157733.1 with this.But in the patent of the disclosure, there is no perfect whole membrane integrating technique (comprising the membrane techniquies such as removal of impurities, ceramic membrane ultrafitration and nanofiltration), more there is no detailed technical process, what is more important, maceration liquid concentration after nanofiltration is concentrated is low, is only 7 ~ 30g/L, can not meet the requirement of extraction process.
Summary of the invention
The purpose of this utility model is the defect that overcomes conventional ion type rare-earth mineral extraction process, extraction process by membrane separation and integration technology for ion type rareearth ore, to replace the techniques such as carbon ammonium precipitation in traditional rare earth extraction process, dry, calcination, acid be molten, provide that a kind of less investment cost is low and floor space is little, be simple and easy to the barrier separation integral process of continuous and automatic operation, and by concentrated to the height of rare earth ion, to solve the low problem of maceration liquid Rare Earth Ion concentration of being brought because of the rare-earth mineral of more and more dilution.Adopt this technique, impurity removal process and ceramic membrane ultrafitration technique are in conjunction with removing accurately suspended contamination in maceration liquid, avoided on the one hand in maceration liquid foreign matter content too high and in concentration process precipitation cause result that cannot be concentrated, also purified on the other hand maceration liquid, made it in later process, can meet better the needs of extraction process.The clear liquid of ceramic membrane is concentrated through the high power of organic membrane, can directly send to and carry out the single rare earth element of extracting and separating, has greatly simplified technique, has reduced cost.
In traditional Techniques For Extraction of Rare Earths, maceration liquid makes aluminium, iron that precipitation occur by carbon ammonium adjust pH and aluminium, iron etc. are removed in removal of impurities, aluminium in process, iron precipitate is more tiny and be difficult to precipitation, thereby needs very large settling bowl carry out sedimentation removal of impurities, and removal of impurities is not very thorough.And ceramic super-filtering film is in other filtration of high precision level, removal for suspended substance has its unique ability, the high-throughout operation of serialization of ceramic membrane greatly reduces the floor space of removal of impurities operation, and effluent characteristics is very good, turbidity has reached below 0.2NTU, the technique needs that not only met organic membrane nanofiltration, more meet the requirement of Liao Xia road extraction process, avoided the generation of emulsification and flocculation phenomenon in extraction process.
Along with more and more dilution of rare-earth mineral, the rare earth ion concentration of rare earth maceration liquid is also more and more lower, the result of bringing: the one, extract the required maceration liquid measure of unit rare-earth products increasing, not only increased the weight of technique burden, and consumed a large amount of medicaments, increased the extraction cost of unit rare-earth products.The 2nd, due to the limitation of carbon ammonium precipitation rare-earth process, after precipitation in maceration liquid residual certain density rare earth ion, rare earth loss amount total in the maceration liquid of a large amount of volumes increases, and causes rare earth total yield in maceration liquid to decline, rare earth resources waste is serious.And just there is hardly such problem in the concentrated of nanofiltration membrane.High-precision nanofiltration membrane is almost all held back high price rare earth ion, not only in the clear liquid of nanofiltration membrane, contain hardly and have valency rare earth element, and concentrating along with nanofiltration membrane, rare earth ion in maceration liquid will be concentrated to higher concentration, as 60 ~ 70g/L, completely can be in lower road extraction process.
Concrete technical scheme is:
A Techniques For Extraction of Rare Earths based on membrane technique, comprises the steps:
(1) ion adsorption type rare earth ore is carried out to maceration, then maceration liquid is carried out to precipitator method pre-treatment removal of impurities, obtain the maceration liquid of removal of impurities;
(2) maceration liquid is passed through to ultrafiltration membrance filter, obtain ultrafiltrated permeation liquid;
(3) ultrafiltrated permeation liquid is concentrated by nanofiltration membrane, obtain nanofiltration concentrated solution;
(4) nanofiltration concentrated solution is carried out to the extraction of rare earth by extraction process.
In above-mentioned step (1), can adopt the technique of conventional ionic absorption rare-earth mineral maceration, maceration agent can be ammonium chloride, ammonium sulfate or both mixing; The object of ensuing removal of impurities is that the method by precipitating makes aluminium, iron plasma in maceration liquid be converted into precipitation, from maceration liquid, separate, can adopt conventional technique to carry out, such as adopting bicarbonate of ammonia, oxalic acid, ammoniacal liquor etc. to regulate maceration liquid, make aluminium, iron plasma precipitation, generally, make to react after for some time in maceration liquid, precipitation meeting natural subsidence, the maceration liquid using supernatant liquor as removal of impurities is sent to lower step ultrafiltration membrance filter.Preferred impurity removal process is: with ammoniacal liquor, adjust left and right, pH=4 ~ 5, reaction times 15 ~ 30min.
In step (2), ultra-filtration membrane can carry out separation to the impurity remaining in the maceration liquid of removal of impurities, particularly in maceration liquid, do not obtain aluminium, the iron precipitate of abundant sedimentation, in addition, other some impurity in maceration liquid, also can obtain separation effectively such as particle, colloid etc., after these ion remavals, can reduce the foreign matter content in maceration liquid, be conducive to improve purity, the impact of minimizing impurity on subsequent process steps of rare earth.Particularly, when extraction process carries out separation to rare earth, if the impurity level in maceration liquid is few, can effectively prevent emulsification and throw out in extraction step, improve efficiency, the yield of extraction.In ultrafiltration step, preferably adopt ceramic super-filtering film, it has good physical strength, can long-time running, flux stabilized, be easy to clean and membrane flux recovers.Preferred ultrafiltration technology parameter is: constant flow continuous cross-flow filters, and flow is preferably controlled at 150 ~ 500 L/m
2h.Operational condition is: temperature is normal temperature, and pressure is 0.1 ~ 0.5MPa, crossflow velocity 3～6m/s.And with self-timing recoil technique, adopt ceramic membrane to produce water and recoil, recoil is spaced apart 30 min～60 min, and the recoil time is 10～30 s.Ceramic excessive filtration membrane material is aluminum oxide, zirconium white or titanium oxide, and the mean pore size scope of ceramic super-filtering film is 0.02～0.1 μ m.Membrane structure is external-compression type or inner pressed tubulose multi-channel structure.
In step (3), adopt the object of nanofiltration membrane to make the further concentrate of maceration liquid.In traditional technique, maceration liquid is carried out after aluminium, iron to remove impurity by means of precipitation, also need the rare earth in maceration liquid to precipitate further, the solid obtaining is carried out to carry out acid after calcination again molten, with this, obtain the denseer solution containing rare earth ion, this processing step is long, to having relatively high expectations of equipment, place, and owing to there being calcination step, can cause again energy consumption higher; Also there are some traditional technologys not to precipitate-calcination of maceration liquid-sour molten processing, but directly maceration liquid is directly entered to extraction process, but this way is for the very low rare-earth mineral of present grade, can cause the consumption of more extraction agent, and maceration liquid Rare Earth Ion is too low, make the efficiency of extraction step very low.And use nanofiltration membrane the concentration of the rare earth ion in maceration liquid further can be improved, extraction process is sequentially carried out.Preferably, in above-mentioned nanofiltration technique, working pressure is 1 ~ 4MPa, and temperature is 5 ~ 45 ℃.Nanofiltration membrane is organic nanofiltration membrane, and the rejection of organic nanofiltration membrane is wherein under 0.7MPa, to the rejection of 2g/L magnesium sulfate, is 96 ~ 99%.In this technique, can mention 60～70g/L by receiving the rare earth ion concentration of concentrated liquor.
The extraction process of the concentrated solution more solito that nanofiltration is obtained extracts rare earth.
Another object of the present utility model is to provide the device that a kind of ion type rareearth ore extracts, comprise the slurry tank, ultra-filtration membrane circulation tank, the hyperfiltration membrane assembly that connect successively, the per-meate side of described hyperfiltration membrane assembly is connected in ultra-filtration membrane clear liquid tank, the side of holding back of hyperfiltration membrane assembly is connected in ultra-filtration membrane circulation tank, and ultra-filtration membrane clear liquid tank is connected in nanofiltration membrane component.
Further, the side of holding back of hyperfiltration membrane assembly is also connected in plate-and-frame filter press, and the per-meate side of plate-and-frame filter press is connected in ultra-filtration membrane circulation tank.
technique effect
This patent technique, extraction process by membrane separation and integration technology for ion type rareearth ore, the combination of the extraction process by the maceration technique with upstream and downstream, replace traditional complexity and tediously long rare earth extraction process, there is obvious advance, compare with traditional technology, there is following superiority:
1, adopt technique scheme, the utility model obtains following beneficial effect: the utility model provides the extraction process of a kind of membrane integrating technique for ion type rareearth ore, by the removal of impurities of rare earth maceration liquid, ceramic membrane ultrafitration, the organic integration of organic membrane nanofiltration technique are got up, replace traditional rare-earth precipitation, dry, calcination and sour molten operation, adopt ceramic membrane ultrafitration operation as the pretreatment process of nanofiltration, the high concentration multiple that has greatly guaranteed nanofiltration process carries out, re dip solution can be concentrated to 60 ~ 70g/L, meet the requirement of Liao Xia road extraction process.By the combination with extraction process, greatly simplified the technological process of production.
2, the utility model passes through the removal of impurities of film and concentrates, not only purifying rare earth maceration liquid, improved the quality of rare-earth products, and concentrated by the high power of film, greatly reduce the production treatment capacity in technological process, improved production efficiency, reduced production cost, before ceramic membrane ultrafitration, add removal of impurities operation, reduced in maceration liquid the concentration impurity ions such as aluminium, iron, guaranteed that precipitation does not occur for these foreign ions in nanofiltration process and the carrying out that disturb nanofiltration process.
3, the high precision of nanofiltration membrane of the present utility model is concentrated, and what can guarantee film sees through liquid Rare Earth Ion concentration below 0.01g/L, even substantially, not containing rare earth ion, has improved widely rare earth yield, has reduced the loss of traditional technology middle-weight rare earths.
4, before ceramic membrane ultrafitration, add removal of impurities operation, through impurity and purification maceration liquid there is not emulsification when the extraction process, there is not throw out.
5, simultaneously, the utility model adopts this not sepn process of undergoing phase transition of film, the energy consuming in whole technique is lower, the high energy consumption that more there is no dry and calcination, and there is no sour molten operation, and both saved a large amount of medicaments and energy, be conducive to again environmental protection, whole nanofiltration see through liquid can direct reuse in maceration process, because of but a typical environmental protection technique.
6, membrane filter appts of the present utility model, compact construction, floor space is little, again can serialization automatic operating, reduced equipment usable floor area and artificial cost of use.
Accompanying drawing explanation
Fig. 1 is the utility model process flow sheet.
Wherein, 1-charging pump, 2-slurry tank, 3-ultra-filtration membrane circulation tank, 4-ultra-filtration membrane recycle pump, 5-hyperfiltration membrane assembly, 6,8,12,13-pneumavalve, 7-plate-and-frame filter press, 9-ultra-filtration membrane clear liquid tank, 10-nanofiltration recycle pump, 11-nanofiltration membrane component.
Embodiment
reference examples
The ion adsorption type rare earth ore of Jiangxi Rare-earth Mine is carried out to maceration, the maceration agent adopting is that ammonium chloride and ammonium sulfate are by the mixture of 1:1, content of rare earth in the maceration liquid obtaining is 0.12 g/L, use ammoniacal liquor to regulate pH to 5, the impurity such as aluminium, iron are carried out to precipitator method removal of impurities, re-using oxalic acid precipitates rare earth ion, solid to gained is dried, after calcination, obtain rare earth ore concentrate, re-use hydrochloric acid and carry out sour molten processing, obtain the solution that contains rare earth chloride, use naphthenic acid extraction agent to carry out the extracting and separating of single rare earth.The flocculation, the emulsion that in extraction process, occur a little.
embodiment 1
As shown in Figure 1, a kind of membrane sepn integrating device in ion type rareearth ore rare earth extraction process that is applied to described in the utility model, structure is:
Comprise the charging pump 1, slurry tank 2, ultra-filtration membrane circulation tank 3, ultra-filtration membrane recycle pump 4, the hyperfiltration membrane assembly 5 that connect successively, the per-meate side of described hyperfiltration membrane assembly 5 is connected in ultra-filtration membrane clear liquid tank 9, the side of holding back of hyperfiltration membrane assembly 5 is connected in ultra-filtration membrane circulation tank 3, ultra-filtration membrane clear liquid tank 9 is connected in nanofiltration membrane component 11 by nanofiltration recycle pump 10, the side of holding back of hyperfiltration membrane assembly 5 is also connected in plate-and-frame filter press 7, and the per-meate side of plate-and-frame filter press 7 is connected in ultra-filtration membrane circulation tank 3; The holding back of side and the saturating side of side, nanofiltration membrane component 11 of holding back at hyperfiltration membrane assembly 5 is respectively arranged with pneumavalve 6,8,12,13 in side and per-meate side.
Maceration is carried out in ionic adsorptive type rare earth ore deposit to Jiangxi Rare-earth Mine, the same reference examples of maceration technique, the maceration agent adopting be ammonium chloride and ammonium sulfate by the mixture of 1:1, the content of rare earth of the maceration liquid obtaining is 0.12 g/L, and maceration liquid pump is entered to remove the gred in the slurry tank 2 of use, with ammoniacal liquor b, regulate pH=5 left and right, after reaction 20min, get supernatant liquor and enter hyperfiltration membrane assembly 5 and carry out solid-liquid separation, ultra-filtration membrane adopts ceramic super-filtering film, material is aluminum oxide, the mean pore size 0.1 μ m of ceramic super-filtering film.Hyperfiltration membrane assembly 5 carries out constant flow filtration, and controlled filter flux is 350 L/m
2h, pressure is 0.3MPa, crossflow velocity 3 m/s, and be provided with recoiling device, and adopting ceramic membrane to produce water and recoil, recoil is spaced apart 40 min, and the recoil time is 20 s.Clear liquid enters into nanofiltration membrane component 11 and concentrates, when the solid content of the concentrated solution of ultra-filtration membrane is 15%, adopt plate-and-frame filter press 7 to process after deslagging.In nanofiltration operation, nanofiltration membrane, under 0.7MPa, is 98% to the rejection of 2g/L magnesium sulfate.Ceramic membrane clear liquid is carried out to 400 times of perseverances of cycles of concentration 11 li of nanofiltration membrane components and concentrate, nanofiltration technique working pressure is 3.8MPa, and temperature is 30 ℃.In the concentrated solution obtaining, rare earth ion concentration reaches 60g/L, then enters into extraction process.In extraction process, there is not emulsification, flocculation phenomenon.Compare with reference examples, rare earth total yield has improved 15%.
Adopt device as shown in Figure 1.
Maceration is carried out in ionic adsorptive type rare earth ore deposit to Yunnan Rare-earth Mine, the same reference examples of maceration technique, the maceration agent adopting is that ammonium chloride and ammonium sulfate are by the mixture of 1:1, the content of rare earth of the maceration liquid obtaining is 0.12 g/L, maceration liquid pump is entered to remove the gred in the slurry tank 2 of use, with ammoniacal liquor b, regulate pH=4 left and right, after reaction 15min, getting supernatant liquor enters hyperfiltration membrane assembly 5 and carries out solid-liquid separation, ultra-filtration membrane adopts ceramic super-filtering film, material is zirconium white, and the mean pore size of ceramic super-filtering film is 0.05 μ m.Hyperfiltration membrane assembly 5 carries out constant flow filtration, and controlled filter flux is 500 L/m
2h, pressure is 0.5 MPa, crossflow velocity 6 m/s, and be provided with recoiling device, and adopting ceramic membrane to produce water and recoil, recoil is spaced apart 30 min, and the recoil time is 30s.Clear liquid enters into nanofiltration membrane component 11 and concentrates, when the solid content of the concentrated solution of ultra-filtration membrane is 15%, adopt plate-and-frame filter press 7 to process after deslagging.In nanofiltration operation, nanofiltration membrane, under 0.7MPa, is 99% to the rejection of 2g/L magnesium sulfate.Ceramic membrane clear liquid is carried out to 400 times of perseverances of cycles of concentration 11 li of nanofiltration membrane components and concentrate, nanofiltration technique working pressure is 4MPa, and temperature is 5 ℃.In the concentrated solution obtaining, rare earth ion concentration reaches 70g/L, then enters into extraction process.In extraction process, there is not emulsification, flocculation phenomenon.Compare with reference examples, rare earth total yield has improved 20%.
Adopt device as shown in Figure 1.
Maceration is carried out in ionic adsorptive type rare earth ore deposit to Yunnan Rare-earth Mine, the same reference examples of maceration technique, the maceration agent adopting be ammonium chloride and ammonium sulfate by the mixture of 1:1, the content of rare earth of the maceration liquid obtaining is 0.12 g/L, and maceration liquid pump is entered to remove the gred in slurry tank 2, with ammoniacal liquor b, regulate pH=5 left and right, after reaction 30min, get supernatant liquor and enter hyperfiltration membrane assembly 5 and carry out solid-liquid separation, ultra-filtration membrane adopts ceramic super-filtering film, material is titanium oxide, and the mean pore size of ceramic super-filtering film is 0.02 μ m.Hyperfiltration membrane assembly 5 carries out constant flow filtration, and controlled filter flux is 150 L/m
2h, pressure is 0.1MPa, crossflow velocity 3 m/s, and be provided with recoiling device, and adopting ceramic membrane to produce water and recoil, recoil is spaced apart 60 min, and the recoil time is 10 s.Clear liquid enters into nanofiltration membrane component 11 and concentrates, when the solid content of the concentrated solution of ultra-filtration membrane is 15%, adopt plate-and-frame filter press 7 to process after deslagging.In nanofiltration operation, nanofiltration membrane, under 0.7MPa, is 98% to the rejection of 2g/L magnesium sulfate.Ceramic membrane clear liquid is carried out to 400 times of perseverances of cycles of concentration 11 li of nanofiltration membrane components and concentrate, nanofiltration technique working pressure is 4MPa, and temperature is 45 ℃.In the concentrated solution obtaining, rare earth ion concentration reaches 65g/L, then enters into extraction process.In extraction process, there is not emulsification, flocculation phenomenon.Compare with reference examples, rare earth total yield has improved 18%.
Claims (6)
1. the ion type rareearth ore extraction element based on membrane technique, comprise the slurry tank (2), ultra-filtration membrane circulation tank (3), the hyperfiltration membrane assembly (5) that connect successively, the per-meate side of described hyperfiltration membrane assembly (5) is connected in ultra-filtration membrane clear liquid tank (9), the side of holding back of hyperfiltration membrane assembly (5) is connected in ultra-filtration membrane circulation tank, and ceramic membrane clear liquid tank (9) is connected in nanofiltration membrane component (11).
2. the ion type rareearth ore extraction element based on membrane technique according to claim 1, it is characterized in that: the side of holding back of described hyperfiltration membrane assembly (5) is also connected in plate-and-frame filter press (7), and the per-meate side of plate-and-frame filter press (7) is connected in ceramic membrane circulation tank (3).
3. the ion type rareearth ore extraction element based on membrane technique according to claim 1, is characterized in that: described ultra-filtration membrane is ceramic membrane.
4. the ion type rareearth ore extraction element based on membrane technique according to claim 3, is characterized in that: described described ceramic membrane is aluminum oxide, zirconium white or oxidation titanium film.
5. the ion type rareearth ore extraction element based on membrane technique according to claim 3, is characterized in that: described Average Pore Size of UF Membrane scope is 0.02～0.1 μ m.
6. the device that ion type rareearth ore according to claim 1 extracts, is characterized in that: described nanofiltration membrane, under 0.7MPa, is 98 ~ 99% to the rejection of 2g/L magnesium sulfate.
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