Extraction of palladium (II) from nitric acid medium by imidazolium nitrate immobilized resin
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VEREGEN TM 12 3 4 5 6 78 910111213141516171819202122(sinecatechins)Ointment, 15%Rx OnlyFor Topical Dermatologic Use OnlyNot for Ophthalmic, Oral, Intravaginal, or Intra-anal UseDESCRIPTIONVeregen TM is a botanical drug product for topical use. The drug substance in Veregen™ is sinecatechins, which is a partially purified fraction of the water extract of green tea leaves from Camellia sinensis (L.) O Kuntze, and is a mixture of catechins and other green tea components. Catechins constitute 85 to 95% (by weight) of the total drug substance which includes more than 55% of Epigallocatechin gallate (EGCg), other catechin derivatives such as Epicatechin (EC), Epigallocatechin (EGC), Epicatechin gallate (ECg) and some additional minor catechin derivatives i.e. Gallocatechin gallate (GCg), Gallocatechin (GC), Catechin gallate (Cg), and Catechin (C). In addition to the known catechin components, it also contains gallic acid, caffeine, and theobromine which together constitute about 2.5% of the drug substance. The remaining amount of the drug substance contains undefined botanical constituents derived from green tea leaves. The structural formulae of catechins are shown below.General Structure of Catechins23242526272829303132333435363738Each gram of the ointment contains 150 mg of sinecatechins in a water free ointment base consisting of isopropyl myristate, white petrolatum, cera alba (white wax), propylene glycol palmitostearate, and oleyl alcohol.CLINICAL PHARMACOLOGYPharmacodynamicsThe mode of action of Veregen TM Ointment, 15% involved in the clearance of genital and perianal warts is unknown. In vitro, sinecatechins had anti-oxidative activity; the clinical significance of this finding is unknown.PharmacokineticsThe pharmacokinetics of topically applied Veregen™ Ointment has not been sufficiently characterized at this time. However, data suggest that systemic exposure to catechins after repeated topical application of Veregen™ Ointment 15% is likely to be less than observed after a single oral intake of 400ml green tea.CLINICAL STUDIES 3940414243444546474849505152535455 Two Phase 3 randomized, double-blind, vehicle-controlled studies were performed to investigate the safety and efficacy of Veregen TM Ointment in the treatment of immunocompetent patients 18 years of age and older with external genital and perianalwarts. The subjects applied the ointment 3 times daily for up to 16 weeks or until complete clearance of all warts (baseline and new warts occurring during treatment).Over both studies the median baseline wart area was 51 mm2 (range 12 to 585 mm2), andthe median baseline number of warts was 6 (range 2 to 30).The primary efficacy outcome measure was the response rate defined as the proportion of patients with complete clinical (visual) clearance of all external genital and perianal warts (baseline and new) by week 16, presented in Tables 1 and 2 for all randomized subjects dispensed medication.Table 1: Efficacy by Region Table 2. Efficacy by GenderCompleteClearanceCompleteClearanceAll Countries(includes the United States)MalesVeregen TM 15% (N = 397) 213 (53.6%) Veregen TM 15% (N = 205) 97(47.3%)Vehicle (N = 207) 73 (35.3%) Vehicle (N = 118) 34(28.8%) United States FemalesVeregen TM 15% (N = 21) 5 (23.8%) Veregen TM 15% (N = 192) 116(60.4%)Vehicle (N = 9) 0 (0.0%) Vehicle (N = 89) 39(43.8%)565758596061626364656667686970 .Median time to complete wart clearance was 16 weeks and 10 weeks, respectively, in the two phase 3 clinical trials.The incidence rate of recurrence of external genital and perianal warts after treatment in patients with complete clearance is unknown.INDICATION AND USAGEVeregen TM is indicated for the topical treatment of external genital and perianal warts (Condylomata acuminata) in immunocompetent patients 18 years and older.CONTRAINDICATIONSVeregen TM is contraindicated in individuals with a history of sensitivity reactions to any of the components of the ointment. In case of hypersensitivity, treatment should be discontinued.WARNINGS 7172737475767778798081828384858687888990919293949596979899 100 101 102 103 104 105 106 107 108 109 110 111 112 113 Veregen TM has not been evaluated for the treatment of urethral, intra-vaginal, cervical, rectal, or intra-anal human papilloma viral disease and should not be used for the treatment of these conditions.PRECAUTIONSGeneralUse of Veregen TM on open wounds should be avoided.The safety and efficacy of Veregen TM in immunosuppressed patients have not been established.Safety and efficacy have not been established for Veregen TM in the treatment of external genital and perianal warts beyond 16-weeks or for multiple treatment courses.Patients should be advised to avoid exposure of the genital and perianal area to sun/UV-light as Veregen TM has not been tested under these circumstances.Information for PatientsGeneral InformationPatients using Veregen TM should receive the following information and instructions:1. This medication is only to be used as directed by a physician. It is for external useonly. Eye contact should be avoided as well as application into the vagina or anus.2. It is not necessary to wash off Veregen TM prior to the next application. When thetreatment area is washed or a bath is taken, the ointment should be applied afterwards.3. It is common for patients to experience local skin reactions such as erythema,erosion, edema, itching, and burning at the site of application. Severe skin reactions can occur and should be promptly reported to the healthcare provider.Should severe local skin reaction occur, the ointment should be removed by washing the treatment area with mild soap and water and further doses held.4. Sexual (genital, anal or oral) contact should be avoided while the ointment is onthe skin, or the ointment should be washed off prior to these activities. Veregen TM may weaken condoms and vaginal diaphragms. Therefore the use in combination with Veregen TM is not recommended.5. Female patients using tampons should insert the tampon before applying theointment. If the tampon is changed while the ointment is on the skin, accidental application of the ointment into the vagina must be avoided.6. Veregen TM may stain clothing and bedding.7. Veregen TM is not a cure and new warts might develop during or after a course oftherapy. If new warts develop during the 16 –week treatment period, these should also be treated with Veregen TM.8. The effect of Veregen TM on the transmission of genital/perianal warts is unknown.9. Patients should be advised to avoid exposure of the genital and perianal area tosun/UV light as Veregen TM has not been tested under these circumstances.114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 15710. The treatment area should not be bandaged or otherwise covered or wrapped as tobe occlusive.11. Uncircumcised males treating warts under the foreskin should retract the foreskinand clean the area daily.Carcinogenesis, Mutagenesis, Impairment of FertilityThe Maximum Recommended Human Dose (MRHD) of Veregen TM Ointment, 15%was set at three times daily topical administration of 250 mg, 750 mg total, containing 112.5 mg sinecatechins for the animal multiple of human exposure calculations presented in this labeling. Dose multiples were calculated based on the human equivalent dose (HED).In an oral (gavage) carcinogenicity study, sinecatechins was administered daily for 26 weeks to p53 transgenic mice at doses up to 500 mg/kg/day (22-fold MRHD). Treatment with sinecatechins was not associated with an increased incidence of either neoplastic or non-neoplastic lesions in the organs and tissues examined. Veregen TM Ointment, 15% has not been evaluated in a dermal carcinogenicity study.Sinecatechins was negative in the Ames test, in vivo rat micronucleus assay, UDS test, and transgenic mouse mutation assay, but positive in the mouse lymphoma mutation assay.Daily vaginal administration of Veregen TM Ointment, 15% to rats from Day 4 before mating and throughout mating until Day 17 of gestation did not cause adverse effects on mating performance and fertility at doses up to 0.15 mL/rat/day. This dose corresponds to approximately 150 mg/rat/day (8-fold MRHD).Pregnancy Category: CEmbryo-fetal development studies were conducted in rats and rabbits using intravaginal and systemic routes of administration, respectively. Oral administration of sinecatechins during the period of organogenesis (gestational Days 6 to 15 in rats or 6 to 18 in rabbits) did not cause treatment related effects on embryo-fetal development or teratogenicity at doses of up to 1,000 mg/kg/day (86-fold MRHD in rats; 173-fold MRHD in rabbits).In the presence of maternal toxicity (characterized by marked local irritation at the administration sites and decreased body weight and food consumption) in pregnant female rabbits, subcutaneous doses of 12 and 36 mg/kg/day of sinecatechins during the period of organogenesis (gestational Days 6 to 19) resulted in corresponding influences on fetal development including reduced fetal body weights and delays in skeletal ossification. No treatment related effects on embryo-fetal development were noted at 4 mg/kg/day (0.7-fold MRHD). There was no evidence of teratogenic effects at any of the doses evaluated in this study.A combined fertility / embryo-fetal development study using daily vaginal administration of Veregen TM Ointment, 15% to rats from Day 4 before mating and throughout mating158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198 until Day 17 of gestation did not show treatment-related effects on embryo-fetal development or teratogenicity at doses up to 0.15 mL/rat/day (8-fold MRHD).A pre- and post-natal development study was conducted in rats using vaginal administration of Veregen TM Ointment, 15% at doses of 0.05, 0.10 and 0.15 mL/rat/day from Day 6 of gestation through parturition and lactation. The high and intermediate dose levels of 0.15 (8-fold MRHD) and 0.10 mL/rat/day resulted in an increased mortality of the F0 dams, associated with indications of parturition complications. The high dose level of 0.15 mL/rat/day also resulted in an increased incidence of stillbirths. There were no other treatment-related effects on pre- and post-natal development, growth, reproduction and fertility at any dose tested.There are no adequate and well-controlled studies in pregnant women. Veregen TM Ointment, 15% should be used during pregnancy only if the potential benefit justifies the potential risk to the fetus.Nursing MothersIt is not known whether topically applied Veregen TM is excreted in breast milk.Pediatric UseSafety and efficacy in pediatric patients have not been established.Geriatric useSeven patients (1.4%), older than 65 years of age were treated with Veregen TM in clinical studies. This, however, is an insufficient number of subjects to determine whether they respond differently from younger subjects.ADVERSE REACTIONSAdverse Events / Local Skin ReactionsIn Phase 3 clinical trials, a total of 397 subjects received Veregen™Ointment, 15% three times per day topical application for the treatment of external genital and perianal warts for up to 16 weeks.Serious local adverse events of pain and inflammation were reported in two subjects (0.5%), both women.In clinical trials, the incidence of local adverse events leading to discontinuation or dose interruption (reduction) was 5% (19/397). These included the following events: application site reactions (local pain, erythema, vesicles, skin erosion/ulceration), phimosis, inguinal lymphadenitis, urethral meatal stenosis, dysuria, genital herpes simples, vulvitis, hypersensitivity, pruritus, pyodermitis, skin ulcer, erosions in the urethral meatus, and superinfection of warts and ulcers.199 200 201 202 203 204 205 206 207 Because clinical trials are conducted under widely varying conditions, adverse reaction rates observed in the clinical trials of a drug cannot be directly compared to rates in the clinical trials of another drug and may not reflect rates observed in practice.Local and regional reactions (includes adenophathy) occurring at >1% in the treated group are presented in Table 3.Table 3: Local and Regional Adverse Reactions DuringTreatment (% Subjects)Veregen™(N=397)Vehicle(N=207)Erythema7032Pruritus6945Burning6731Pain/discomfort56 14Erosion/Ulceration49 10Edema4511 Induration3511Rash vesicular 20 6Regional Lymphadenitis 3 1Desquamation5<1Discharge3<1Bleeding2<1 Reaction2Scar10 Irritation1Rash1208209 210 211 212 213 214 215 216 217 218 219 220 221 222 223 224 A total of 266/397 (67%) of subjects in the Veregen™, 15% group had either a moderate or a severe reaction that was considered probably related and of these 120 (30%) subjects had a severe reaction. Severe reactions occurred in 37% (71/192) of women and in 24% (49/205) of men. The percentage of subjects with at least one severe, related adverse event was 26% (86/328) for subjects with genital warts only, 42% (19/45) in subjects with both genital and perianal warts and 48% (11/23) of subjects with perianal warts only.Phimosis occurred in 3% of uncircumcised male subjects (5/174) treated with Veregen™ and in 1% (1/99) in vehicle.The maximum mean severity of erythema, erosion, edema and induration was observed by week 2 of treatment.Less common local adverse events included urethritis, perianal infection, pigmentation changes, dryness, eczema, hyperesthesia, necrosis, papules, and discoloration. Other less225226227228229230231 232 233234 235 236237238239240241242243244245246247248249250251 252 253254 255 256257 258259 260261 262 263264265 266 common adverse events included cervical dysplasia, pelvic pain, cutaneous facial rash and staphylococcemia.In a dermal sensitization study of Veregen™ Ointment in healthy volunteers, hypersensitivity (type IV) was observed in 5 out of 209 subjects (2.4%) under occlusive conditions.OVERDOSAGEOverdosage with Veregen TM has not been reported.DOSAGE AND ADMINISTRATIONVeregen TM Ointment, 15% is to be applied three times per day to all external genital and perianal warts.It is recommended to wash the hands before and after application of Veregen TM. About a 0.5 cm strand of the Veregen TM Ointment, 15% should be applied to each wart using the finger(s), dabbing it on to ensure complete coverage and leaving a thin layer of the ointment on the warts.It is not necessary to wash off the ointment from the treated area prior to the next application.Treatment with Veregen TM should be continued until complete clearance of all warts, however no longer than 16 weeks.Local skin reactions (e.g. erythema) at the treatment site are frequent. Nevertheless, treatment should be continued when the severity of the local skin reaction is acceptable. HOW SUPPLIEDVeregen TM Ointment, 15% is a brown ointment and is supplied in aluminium tubes containing 15 gram ointment per tube.Storage ConditionsPrior to dispensing to the patient, store refrigerated 2°C to 8°C (36°F to 46°F). After dispensing, store refrigerated or up to 25°C (77°F). Do not freeze.Keep out of reach of childrenNDC # 10337-450-15The VEREGEN trademark is used by Bradley Pharmaceuticals, Inc. under license from MediGene AG.Manufactured by:267 268 269 270 271 272 C.P.M. Contract Pharma GmbH & Co. KG Frühlingstrasse 7D-83620 Feldkirchen-Westerham GermanyManufactured for:273274 275 276 277 278 279 280 281 383 Route 46 WestFairfield, NJ 07004 2402 USACo-marketed with Kenwood Therapeutics, a division of Bradley Pharmaceuticals, Inc. December 2006PATIENT INFORMATION 123 4 5 6 7 8 9101112131415161718192021222324252627282930313233343536373839404142Veregen™(sinecatechins)Ointment, 15%Rx OnlyRead this leaflet carefully before you start using Veregen™ Ointment, 15% and each time you refill your prescription. There may be new information. This information does not take the place of your doctor’s advice. If you have any questions about Veregen™ Ointment, 15% or your condition ask your doctor or pharmacist. Only your doctor can prescribe Veregen™ and determine if it is right for you.What is Veregen™ Ointment, 15%?Veregen™ Ointment, 15% is a medicine for skin use only (topical) for the treatment of warts on the outside of the genitals and around the outside of the anus. It is not a treatment for warts in the vagina, cervix, or inside the anus. Your doctor may recommend examination and screening tests (such as a Pap smear) to evaluate these areas.Who should not use Veregen™ Ointment, 15%?Do not use Veregen™ Ointment, 15% if you are allergic to an ingredient in Veregen™ Ointment, 15%. The list of ingredients is at the end of this leaflet.What should I tell my doctor before taking Veregen™ Ointment, 15%?Tell your doctor about all your health conditions and all the medicines you take including prescription, over-the-counter medicine, vitamins, supplements, and herbals. Be sure to tell your doctor if you are:•pregnant or planning to become pregnant, as it is not known if Veregen™ Ointment, 15% can harm your unborn baby. Your doctor will determine whether the benefit outweighs the risk.•breastfeeding, as it is not known if Veregen™ Ointment, 15% can pass into your milk and if it can harm your baby.•using any other type of skin product or have open wounds on the area to be treated. Veregen™ Ointment, 15% should not be used until your skin has healed from other treatments applied to the same area.•immunocompromised. This means that your immune system cannot fight infections as well as it should.4445464748495051525354555657585960616263646566676869707172737475767778798081828384 How should I use Veregen™ Ointment, 15%?•Use Veregen™ Ointment, 15% only on the area affected exactly as prescribed by your doctor.•Wash your hands before and after application of Veregen™ Ointment, 15%.A small amount of the ointment should be applied to all wart using your finger(s),dabbing it on to ensure complete coverage and leaving a thin layer of the ointment on the warts as directed by your doctor.•Apply Veregen™ Ointment, 15%three times per day ---in the morning, at noontime and in the evening.•Do not wash off the ointment from the treated area before the next application.When you wash the treatment area or bathe, apply the ointment afterwards.•Treatment with Veregen™ Ointment, 15% should be continued until complete clearance of all warts, however no longer than 16 weeks. If your warts do not go away, or if they come back after treatment call your doctor.•Veregen™ Ointment, 15% is not a cure for warts on your genitals or around your anus with certainty. New warts may develop during or after treatment, and may need treatment.What should I avoid while using Veregen™ Ointment, 15%?•Do not apply Veregen™ Ointment, 15% on open wounds or into the vagina or into the anus.•Genital warts are a sexually transmitted disease, and you may infect your partner.•Avoid sexual contact (genital, anal or oral) when Veregen™ Ointment, 15% is on your genital or perianal skin. If you do choose to have sexual contact, you must wash off the ointment carefully before having protected sexual contact as the ointment may weaken condoms and vaginal diaphragms. Talk to your doctor about safe sex practices.•Avoid contact with your eyes, nostrils and mouth while ointment is on your finger(s).•Women using tampons: insert the tampon before applying the ointment. If you need to change your tampon while the ointment is on your skin, avoid getting the ointment into the vagina.8687888990919293949596979899 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127•Uncircumcised men treating warts under the foreskin should retract the foreskin and clean the area daily.•Do not expose the genital area treated with Veregen™ Ointment, 15% to sunlight, sunlamps or tanning beds.•Do not cover the treated area. Loose-fitting undergarments can be worn after applying Veregen™ Ointment, 15%.•Veregen™ Ointment, 15% may stain your light colored clothes and bedding. It is recommended to wear darker colored undergarments while using Veregen™ Ointment, 15%.What are the possible side effects of Veregen™ Ointment, 15%?The most common side effects with Veregen™ Ointment, 15%are local skin and application site reactions including:•redness•swelling•sores or blisters•burning•itching•painMany patients experience itching, reddening or swelling on or around the application site during the course of treatment. Some of these side effects could be a sign of an allergic reaction. If you experience open sores or other severe reactions at the locations you applied Veregen™, stop treatment and call your doctor right away.You may experience other side effects of Veregen™ Ointment, 15%, which are not mentioned here. Ask your doctor or pharmacist for more information.Patients should be aware that new warts may develop during treatment as Veregen™ Ointment, 15% is not a cure.How should I store Veregen™ Ointment, 15%?•Store Veregen™ Ointment, 15% refrigerated or up to 77ºF (25 ºC).•Do not freeze.•Make sure the cap on the tube is tightly closed.•Safely throw away Veregen™ Ointment, 15% tubes that are out of date or are empty.Keep Veregen™Ointment, 15% and all medicines out of the reach of children.129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 General advice about prescription medicinesMedicines are sometimes prescribed for conditions that are not mentioned in patient information leaflets. Do not use Veregen™ Ointment, 15% for a condition for which it was not prescribed. Do not give Veregen™ Ointment, 15% to other people, even if they have the same symptoms you have. It may harm them. Do not use Veregen™ Ointment, 15% after the expiration date on the tube.This leaflet summarizes the most important information about Veregen™ Ointment, 15%. If you would like more information, talk with your doctor. You can ask your pharmacist or doctor for information about Veregen™ Ointment, 15% that is written for the doctor.What are the ingredients in Veregen™ Ointment, 15%?Active ingredient:A defined green tea extract named sinecatechins.Inactive ingredients:Isopropyl myristate, white petrolatum, cera alba (white wax), propylene glycol palmitostearate, and oleyl alcohol.Veregen™ is a trademark of MediGene AG, D-82152 Planegg/Martinsried, Germany. Manufactured by: C.P.M. Contract Pharma GmbH & Co. KG, Frühlingstrasse 7, D-83620 Feldkirchen-Westerham, Germany.Manufactured for:156 157 158 159 160 383 Route 46 West Fairfield, NJ 07004 2402 USACo-marketed with:161162163164 December 2006Text for the Outer Carton Label 1NDC # 10337-450-xx 2Rx OnlyVEREGEN TM(sinecatechins) Ointment15%For Topical Dermatologic Use Only.Not for Opthalmic, Oral, Intravaginal, or Intra-anal Use.Keep out of reach of children.Description: Veregen TM is a botanical drug product. The drug substance in Veregen TM is sinecatechins, which is a partially purified fraction of the water extract of green tea leaves of Camellia sinensis (L.) O Kuntze, and is a mixture of catechins, their derivatives and other green tea components.Active ingredient: sinecatechins (150 mg/g).Excipients: isopropyl myristate, white petrolatum, cera alba (white wax), propylene glycol palmitostearate, and oleyl alcohol.Usual Adult dose: See accompanying package insert for full Prescribing Information. Manufactured by: C.P.M. Contract Pharma GmbH & Co. KG, Frühlingstrasse 7, D-83620 Feldkirchen-Westerham, Germany.Manufactured for:383 Route 46 West, Fairfield, NJ 07004-2402 USACo-marketed with Kenwood Therapeutics, a division of Bradley Pharmaceuticals, Inc. Lot:Exp:UPC/Bar CodeYY 3gStore in a refrigerator at 2-8°C (36-46°F) until dispensed to the patient.Patient can store refrigerated or up to 25°C (77°F). Do not freeze.U.S. Patent Nos. 5795911 and 5968973________________________________________________________________________1 Text presented on the outer carton may not appear in the order outlined in this document.2 xx = 15 for the 15g ointment size, xx = 03 for the 30g ointment size3Text for the Immediate Container (Tube) Label 4NDC # 10337-450-xx 5Rx OnlyVeregen TM(sinecatechins) Ointment15%YY 6 gFor Topical Dermatologic Use Only.Not for Opthalmic, Oral, Intravaginal, or Intra-anal Use.Keep out of reach of children. Keep tightly closed.Description: Veregen TM is a botanical drug product. The drug substance in Veregen TM is sinecatechins, which is a partially purified fraction of the water extract of green tea leaves of Camellia sinensis (L.) O Kuntze, and is a mixture of catechins, their derivatives and other green tea components.Active ingredient: sinecatechins (150 mg/g).Excipients: isopropyl myristate, white petrolatum, cera alba (white wax), propylene glycol palmitostearate, and oleyl alcohol.Usual Adult dose: See accompanying package insert for full Prescribing Information.Store in a refrigerator at 2-8°C (36-46°F) until dispensed to the patient.Patient can store refrigerated or up to 25°C (77°F). Do not freeze.For control number and expiration date, see crimp of tube.Manufactured by: C.P.M. Contract Pharma GmbH & Co. KG, Frühlingstrasse 7, D-83620 Feldkirchen-Westerham, Germany.Manufactured for:383 Route 46 West, Fairfield, NJ 07004-2402 USACo-marketed with Kenwood Therapeutics, a division of Bradley Pharmaceuticals, Inc. SAMPLE. NOT FOR SALE. 7U.S. Patent Nos. 5795911 and 5968973________________________________________________________________________4 Text presented on the outer carton may not appear in the order outlined in this document.5 xx = 15 for the 15 g ointment size, xx = 03 for the 30 g ointment size, xx = 99 for the 4 g ointment (physician sample) size.6 YY = 15 for the 15 g ointment size, YY = 30 for the 30 g ointment size, YY = 4 for the 4 g ointment (physician sample) size.7 This statement only applicable for the 4 g ointment (physician sample) size.。
Ž.Hydrometallurgy511999239–253Recovery of titanium from the leach liquors oftitaniferous magnetites by solvent extractionPart1.Review of the literature and aqueousthermodynamicsKathryn C.Sole)Hydrometallurgy DiÕision,Mintek,PriÕate Bag X3015,Randburg2125,South AfricaReceived10August1998;revised28November1998;accepted2December1998AbstractSouthern African titaniferous magnetites from the Bushveld Complex provide a potential source of titanium,vanadium,and iron.Traditional approaches to recovering these metals have involved pyrometallurgical techniques:more recently,however,the use of hydrometallurgical routes is receiving attention.If the species of interest can be adequately solubilized by sulphuric acid,solvent extraction may enable high-purity solutions of titanium and vanadium to be produced.These could then be processed via a precipitation route to produce saleable oxide products.This review evaluates the open literature with respect to the aqueous chemistry and solvent extraction of titanium in acidic sulphate media.Some observations concerning the technical feasibility of this approach for the treatment of acidic sulphate liquors produced from the leaching of titaniferous magnetites are also presented.q1999Elsevier Science B.V.All rights reserved.Keywords:Titanium;Leach liquors;Titaniferous magnetites;Solvent extraction;Thermodynamics;Bushveld Complex1.IntroductionSouthern African titaniferous magnetites from the Bushveld Complex provide a potential source of titanium,vanadium,and iron.These ores generally comprise a)Fax:q27-11-709-4160;E-mail:kathys@mintek.co.za.0304-386X r99r$-see front matter q1999Elsevier Science B.V.All rights reserved.Ž.PII:S0304-386X9800081-4()K.C.Sole r Hydrometallurgy 511999239–253240magnetite spinel in which titanium is present in solid solution as ilmenite or ulvospinel,and vanadium is in solid solution as the spinel structure coulsonite.Pyrometallurgical approaches have traditionally been employed to recover these elements;however,hydrometallurgical routes are currently also receiving attention.If the elements of interest can be adequately solubilized by sulphuric acid,for example,solvent extraction may offer a viable method of producing high-purity titanium and vanadium solutions of reasonable concentration.These could then be treated by precipitation,followed by calcination,to produce saleable oxide products.This review examines the potential for the recovery of titanium by solvent extraction with particular application to acidic sulphate media.The aqueous chemistry of titanium and its speciation in sulphate media are first reviewed,and the thermodynamic species distribution of a typical sulphuric acid leach liquor is modelled.An evaluation of the literature pertaining to the solvent extraction recovery of titanium from sulphate media is then presented.Finally,some observations concerning the technical feasibility of this approach to the treatment of titaniferous magnetite acidic sulphate leach liquors are made.2.Aqueous chemistry of titanium in acidic sulphate media2.1.Titanium speciesThe precise compositions of the aqueous titanium species that occur in acid media w x remain controversial 1,particularly because of difficulties in achieving thermodynamic w x equilibrium in these systems.The Ti–H O stability diagram of Pourbaix 2is repro-23q Ž.duced in Fig.1.According to this source,the titanous ion,Ti violet ,and titanyl ion,2q Ž.TiO colourless ,are formed in non-oxidizing strong acids.The existence of the titanyl ion remains unproved,however,and there is debate about whether the divalentŽ.2q Ž.2q w x titanium IV ion is TiO or Ti OH 3.The extent to which hydrolysis occurs 2remains similarly unresolved,although this phenomenon appears to become important w x above pH 0.74:TiO 2q q H O °TiO OH q q H q 1Ž.Ž.22qq q Ti OH q H O °Ti OH q H .2Ž.Ž.Ž.232The titanium hydrolysis reactions for which stability constants have been measured are w x given in Table 15–7.w x w x Nabivanets et al.5,8,9and Babko et al.10have studied the aqueous chemistry of titanium by electromigration,ion-exchange chromatography,and dialysis techniques.They have shown that in acid at pH -1.3,in the absence of complex-forming reagents,2q w x titanium is present as monomeric divalent cations,assumed to be TiO 5,9.In sulphate solutions,titanium forms electrically neutral and anionic complexes,since the SO 2y and HSO y ions take part in complex formation.In sulphuric acid,species such as44()K.C.Sole r Hydrometallurgy 511999239–253241Ž.Fig.1.Potential-pH equilibrium diagram for the titanium–water system at 258C and a Ti s 0.2M,established Ž.considering the hydroxide Ti OH and hydrated oxide TiO P H O as the derivatives of tri-and tetravalent 322Žw x .titanium adapted from the work of Pourbaix 2.w Ž.x 2y w Ž.x 4y TiOSO ,TiO SO ,and TiO SO form with increasing sulphate concentra-44244w x tion 4,5,8,9:TiO 2q q SO 2y°TiOSO 3Ž.442y2y TiOSO q SO °TiO SO 4Ž.Ž.44422y2y2y q TiO SO q SO q 2H °Ti SO q H O5Ž.Ž.Ž.444223The species distribution diagram as a function of sulphate concentration proposed by w x Ž.Nabivanets 8is reproduced in Fig.2a .Ž.Ž.qThe species Ti OH HSO and Ti OH HSO are also believed to be present in 3424w x Ž.sulphate media 3,11.Fig.2b shows the distribution diagram proposed by Beukenkamp w x and Herrington 11,in which the hydrated titanium species are seen to play a more prominent role than proposed by the Russian workers.Table 2lists published stability w x constants for aqueous-phase reactions between titanium and sulphate species 7,8,11,12.The dominant species in sulphuric acid is TiOSO P 2H O,represented more accu-42Ž.rately as Ti OH HSO .This structure consists of an infinite zigzag of –Ti–O–Ti–O–34chains.Titanium is octahedrally coordinated by two bridging oxygen atoms,an oxygen w x atom from each of three sulphate ions,and one water molecule 13.Evidence presented Ž.by several investigators indicates that polymerized titanium IV species exist in aqueous w x w x sulphate media 14–18.Kadyrova and Ivanova 16have found the maximum concen-tration of polyions to occur at sulphuric acid concentrations of 1.4to 1.6M.At higher()K.C.Sole r Hydrometallurgy 511999239–253242Table 1Hydrolysis reactions of titanium ReactionStability constant References 3q q q w x Ti q H O °TiO q 2H log b sy 4.5723q y 2qŽ.w x Ti q OH °Ti OH log K s 11.583q y 4qŽ.w x 2Ti q 2OH °Ti OH log K s 24.88222q qqŽ.w x TiO q H O °TiO OH q H log K s 12.8252q q 2q Ž.Ž.w x Ti OH q H °Ti OH log K s 0.3532y 4y nŽ.Ž.w xTi OH q OH °Ti OH log K s 14.707n y 1n1log K s 14.322log K s 14.053log K s 13.7442q y 2qy w x TiO q HO °TiO HO log b s 12.297222q 2q TiO q H O °TiO H O log b s 3.7122222y 2y nq Ž.w xTi O q n H O °Ti O OH q n H log b sy 2.53725225n1log b sy 4.582log b sy 8.73log b sy 14.34log b sy 21.55logb sy 30.06concentrations,the polymeric species are destroyed,and at 5to 8M monomeric species ŽŽ.Ž..Ž.predominate Eqs.3–5.The reaction scheme for the polymerization of titanium IV w x in sulphate solutions has been written 15,16:2TiOSO °TiOSO 6Ž.Ž.4422TiO SO °TiO SO .7Ž.Ž.Ž.44222w x It has been suggested 14,16that the most probable structure of the dimers is a cyclic arrangement in which the titanium atoms are connected by oxygen bridges.Since four-membered rings are more strained than five-or six-membered rings,it is under-standable why the dimers are destroyed as the sulphate concentration is increased.As w Ž.2q x discussed in Section 3.1,evidence for a polymerized TiO structure in the aqueous n phase has also been obtained from solvent extraction data.3q Ž.2q Ž.4q qAs regards trivalent titanium,the hydrated ions Ti ,Ti OH ,Ti OH ,TiO ,22Ž.q w x Ti OH ,and other hydroxocomplexes can exist in solution,depending on the pH 19.2Under the typical conditions of pH and potential existing in sulphate leach liquors,Ž.Ti III is unlikely to be present in significant amounts.2.2.Speciation modelling of titaniferous magnetite leach liquorIn view of the significant discrepancies in the published values of thermodynamic data,speciation modelling was undertaken to assess the validity of the available data,and to determine the distribution of the most probable aqueous species to be found in a typical sulphate liquor produced from the leaching of a titaniferous magnetite.The JESS Žmodel,jointly developed by Water Quality Information Systems at the CSIR South .Ž.w x Africa and Murdoch University Western Australia ,was used 20–22.This model is()K.C.Sole r Hydrometallurgy511999239–253243Fig.2.Distribution of aqueous titanium species as a function of sulphate concentration,adapted from the Ž.w xŽ.w xworks of a Nabivanets8and b Beukenkamp and Herrington11.Žsuited to modelling high ionic strength systems,such as those of leach liquors I f1.5 .Ž.M.All available thermodynamic data Tables1and2were incorporated into the model.2.2.1.Methodology and dataÕerificationTable3gives the chemical analysis of a typical sulphuric acid solution arising fromŽ. the leaching of a titaniferous magnetite from the Brits area North West Province of South Africa.This composition was used for the speciation modelling.The mass balance was completed by assuming that all metals were present in solution as sulphates.An ionic strength of1.47M was calculated.()244K.C.Sole r Hydrometallurgy511999239–253Table2Reactions of titanium in sulphate mediaReaction Stability constant References 2q y q w xTiO q HSO°TiO P HSO log K s2.158443q y y w xTi q SO°TiSO log K s1.001244q yŽ.Ž.w xTi OH q HSO°Ti OH HSO log K s1.0563434q y qŽ.Ž.w xTi OH q HSO°Ti OH HSO log K sy0.19624242q2y w xTiO q SO°TiOSO log K s2.39694412y2yŽ.w xTiOSO q SO°TiO SO log K s2.1979 444222y2y q2yŽ.Ž.TiO SO q SO q2H°Ti SO q H424432Although the thermodynamic data for titanium species were the best available,thevalidity of these data has not been independently verified.The Ti–H O Pourbaix2Ž.diagram Fig.1was reasonably reproduced using the model.The data of Beukenkamp w xand Herrington11were found to represent the Ti–O–SO system far better than those4w xof Nabivanets8.Based on the evaluation of stability constants,titanium hydroxide species are found to predominate in solution even at relatively high acid strengths.It is likely,however, that the rate at which thermodynamic equilibrium is attained is extremely slow and that, in fact,titanium sulphate species do exist in systems of practical interest.In the absence of reliable kinetic data,it is not possible to gauge the extent to which equilibrium has been attained.The following species were omitted from the simulation as the kinetics of4qŽ.3qŽ.2q their formation are expected to be very slow:Ti,Ti OH,TiOH,Ti OH,4Žs.2Ž.Ž.3qŽ.qŽ.Ž.qTi OH,TiH OH,Ti OH,TiH OH SO,TiH OH SO.4233424On excluding the hydroxide species from the model,the dominant titanium speciesŽ.2y q2qare found to be TiOSO,TiO SO,TiOHSO and TiO.The distribution of these4424Žy1. species was simulated as a function of sulphate concentration20to120g l andŽ.electrochemical potential0.4,0.7,and1.0V.2.2.2.Effect of sulphate concentrationThe simulated effect of total sulphate concentration on the speciation of the titanium species in the leach liquor is shown in Fig.3.Of particular significance to the solventTable3Composition of titaniferous magnetite leach liquor used for speciation modellingy1y1Ž.Ž.Species Concentration g l Concentration mol lH SO75.000.76524Fe52.300.936Ti 4.700.098Al 1.700.063V0.930.018Mg0.440.018Cr0.180.003Mn0.130.002()K.C.Sole r Hydrometallurgy511999239–253245Fig. 3.Simulation modelling of titanium species distribution as a function of sulphate concentration.Conditions:258C,730mV,S added as H SO.24extraction of titanium is the relative distribution of cations,anions,and neutral species, as this will influence the choice of extractant.The proportion of cations is found to increase with increasing sulphate concentration,with a corresponding decrease in the mole fraction of anions and neutral species.2.2.3.Effect of solution potentialThe simulated species distribution of titanium,vanadium,and iron species as a function of solution potential is shown in Table4.The calculated distribution of cations, anions,and neutral species is shown in Table5.As the solution potential increases,the proportion of cations and neutral species increases,while anions decrease.2.2.4.Limitations of speciation modellingIt should be borne in mind that modelling of the current system involves several limitations:Ž.i the high ionic strength of the solution introduces some error into the model,since the thermodynamic data are extrapolated from values measured at low ionic strength,Ž.ii the paucity of aqueous thermodynamic data for titanium,and the fact that it has not been independently validated and is not always self-consistent,Ž.iii the solution is unlikely to exist in a state of thermodynamic equilibrium,and therefore the thermodynamically most stable species may not actually be present in solution.Despite the limitations in interpretation introduced by these constraints,these simula-Ž. tions nevertheless provide a starting point from which to consider the class es of solvent extraction reagents that could be considered for the selective removal of titanium from iron and vanadium.In particular,the rather unusual distribution of titanium()246K.C.Sole r Hydrometallurgy511999239–253Table4Simulated effect of potential on species distribution in titaniferous magnetite leach liquorMetal Species Mass%0.4V0.7V 1.0V2qIron Fe373qFeHSO3314FeSO3024Ž.FeH SO464842yŽ.Fe SO192042qFeSO161842qFeHSO894FeOHSO3343qFe122yŽ.Titanium TiO SO52484742qTiOHSO4045464TiOSO35543qTi2qTiSO14yŽ.Ti SO1422qTiO122Vanadium VOSO6171843qV16qVOHSO119142qVO112qVSO243qVO20yVO SO4624qVO422Conditions:258C,pH0.06.between cationic,anionic,and neutral species suggests that possible difficulties may arise in achieving quantitative extraction with a single reagent.Table5Distribution of cations,anions,and neutral species in titaniferous magnetite leach liquor as a function of electrochemical potentialŽ.Ž.Ž.Ž.Metal Potential V Cations%Anions%Neutral species% Titanium0.443.953.1 3.00.746.948.5 4.71.047.847.4 4.8Vanadium0.438.90.061.10.729.20.070.81.045.746.37.9Iron0.470.50.029.60.731.619.952.61.029.220.552.0Conditions:258C,pH0.06.()K.C.Sole r Hydrometallurgy 511999239–2532473.Solvent extractionŽ.w x A critical review of published data on the extraction of Ti IV appeared in 199323.This analysis showed that titanium extraction depends strongly on the acidity of the aqueous phase,and that a bimodal distribution exists:extraction increases with increas-ing acidity,reaching a maximum at acidities below 0.1M,then decreases to a minimum,and increases to a second maximum at acidities above 4M.These observations are significant because acidity can affect phase miscibility,may provide a salting-out effect,and may affect the chemical properties of the extractant.As discussed above,however,the main effect of the acidity is in determining the aqueous-phase speciation of titanium.It was concluded that most extractants are inefficient in regions where TiO 2q dominates Ž.;pH 0,apparently because of the high hydration energy of this species.The dual extraction behaviour for the different classes of extractant is explained by the presence of cationic,anionic,and neutral species present in the aqueous phase under various conditions of acidity.The extractants of interest to the present study are the organophosphorus reagents,which function as cation exchangers,and neutral organophosphorus compounds,which extract neutral species by solvation anophosphorus-acid extractantsŽ.The most common extractant used for titanium is di 2-ethylhexyl phosphoric acid Ž.w x D2EHPA .Iio et al.24studied the kinetics and mechanism of titanium extraction Ž.from nitric acid by D2EHPA represented as the dimer H A .Extraction occurs 22according to the reaction:2qq Ti OH q n H A °Ti OH H A q 2H ,8Ž.Ž.Ž.22222n y 22n where n s 1.5and overlining represents organic-phase species.Stripping was achieved using nitric acid.Titanium has also been extracted from sulphate and chloride media by D2EHPA.w x w x Islam and Biswas 4,25and Islam et al.26have carried out extensive studies of the sulphuric acid system,paying particular attention to the selectivity of titanium over Ž.Ž.Ž.Fe II ,Fe III ,and Mn II .Titanium was found to be extracted as an oligomericpolynuclear complex,with both the HA y and A 2yions acting as ligands:222n q qTiO q n H A ™TiO A q 2n H 9a Ž.Ž.Ž.n n 222n 2n qqTiO q 2n H A ™TiO HA q 2n H 9b Ž.Ž.Ž.Ž.nn 2222n where 1F n F 9.In work carried out under different experimental conditions,the w x molecular formula of the extracted species was found to be TiOA .23w x Islam et al.26also demonstrated that complete equilibration of titanium occurs only after 80to 100min of agitated contact,with the rate of extraction being slow at first,then increasing after about 60min.They postulated that the titanium–oxygen chain splits into smaller chains by the shearing action of the agitation,and that the rate of splitting increases with time.The smaller chains coordinate with the extractant and then()K.C.Sole r Hydrometallurgy 511999239–253248pass into the organic phase.For short contact times,the extent of splitting is small and w Ž.2q x low distribution ratios are observed.Evidence for the existence of polymerized TiO n in the aqueous phase is also shown by the fact that the distribution ratio decreases with increasing metal concentration.From the temperature dependence of the distribution Ž.ratio,these investigators showed that titanium IV forms stronger complexes with Ž.Ž.w x D2EHPA than do Fe II or Fe III 26.Later studies examined the feasibility of using D2EHPA to recover titanium from w x iron in the treatment of ilmenite leach liquors 27.Titanium was optimally extracted at pH 0.9,although some iron was co-extracted.Titanium was then recovered by precipita-tion of TiO from the organic phase using Na CO ,although only 40%recovery was 223w x achieved.In subsequent work 28aimed at decreasing the iron content of the final product,2M HCl was used to strip iron from the loaded organic phase.The stripped aqueous phase was then further purified by extracting the iron using a tributylphos-phate–thiocyanate mixture,prior to precipitation of titania.Recovery of titanium was about 70%,with a purity in excess of 97%.w x Ž.Sato and Nakamura 29have also studied the extraction of Ti IV from sulphate media.Titanium was again found to be extracted as a polymeric complex.At low acidities,the reaction occurs via an ion-exchange mechanism:2qq n Ti OH q n q 1H A °TiO A H q 2n H q n H O.10Ž.Ž.Ž.Ž.2n 222Žn q 1.22At higher acidities,titanium is taken into the organic phase by solvation and the sulphate ion is incorporated into the complex:q yTi OH HSO q HSO q m H A °Ti OH HSO P 2m HA.11Ž.Ž.Ž.Ž.22442242These complex stoichiometries were validated by chemical and spectroscopic analyses.Another extraction system of significance is that involving mono-2-ethylhexylphos-Ž.w x phoric acid M2EHPA 30.This reagent extracts titanium from chloride media with an efficiency three orders of magnitude greater than D2EHPA,and the extraction is independent of the acidity of the aqueous phase in the range of 0.1to 8.8M.It has been suggested that M2EHPA acts as a chelating reagent,rather than by cation exchange,since the reagent is in its protonated form at these acidities.This reagent is also much less sterically hindered than D2EHPA.Titanium is also documented as being extracted by 0.1M dodecylphosphoric acid w x w x Ž.31,by di-o -tolylphosphoric acid 32,and by p -1,1,3,3-tetramethylbutyl phenylphos-w x phoric acid 33.3.2.Neutral organophosphorus compoundsŽ.Tri-n -octylphosphine oxide TOPO is the most widely studied neutral organophos-phorus extractant for titanium.In general,the highest oxidation state of an element Ž.forms the most extractable species in acid–TOPO systems.Ti IV is strongly extracted from H SO ,with extraction enhanced as the acid concentration increases up to 7M 24H SO ;in 8M H SO third-phase formation occurs.This phase is reported to be an 2424adduct of sulphuric acid and TOPO incorporated with water,the diluent,or both.The w x extracted species is postulated to be TiOSO P 2TOPO 34.4Similar to the solvation extraction of titanium by D2EHPA at high acid strengths,extraction by TOPO is reported to be relatively slow,with equilibrium attained only w x after stirring for 20min 34.Sulphuric acid is co-extracted by TOPO to an extent that depends on the acid concentration.At 1M H SO ,0.01mol acid is extracted per mol of TOPO;at 6M 24Ž.w x H SO ,this ratio increases to 0.65Fig.423,24.It was found that the amount of acid 24extracted is independent of the titanium concentration in the aqueous phase.Sato et al.w x 35have identified the organic-phase species H SO P 2TOPO and H SO P TOPO,2424presumed to form according to the reactions:q 2y 2H q SO q 2TOPO °H SO P 2TOPO12a Ž.424q y H SO P 2TOPO q H q HSO °2H SO P TOPO.12b Ž.24424With respect to other elements that may be present in the leach liquors under Ž.Ž.Ž.Ž.Ž.Ž.consideration,it is noted that neither Cu II ,Zn II ,Mn II ,Mg II ,Ca II ,nor Al III w x are extracted from acid sulphate solutions by TOPO 23.Divalent iron is also not Ž.extracted,although Fe II may be partially oxidized when acid solutions are equilibrated with TOPO unless the aqueous phase contains a strong reducing agent and inert Ž.atmosphere.Fe III is extracted by TOPO only from solutions containing the chloride w x Ž.w x Ž.ion 34.Cr III is not extracted from acidic solutions of TOPO 32.Cr VI is extracted from sulphuric acid,but differs from other elements extracted by TOPO in that it is extracted as an anionic species with the approximate composition H Cr O P 2TOPO,227forming an adduct with TOPO in which the phosphoryl oxygen is coordinated with a w x hydrogen atom 34.Kinetics of chromium extraction are rapid.The extraction of Ž.chromium is markedly decreased when the aqueous-to-organic A:O phase ratio is increased,because of the relatively low solubility of the chromic acid adduct inŽFig.4.Extraction of sulphuric acid from aqueous solutions by TOPO adapted from the work of White and w x .Ross 34.Aqueous phase:H SO .Organic phase:10ml 0.1M TOPO in cyclohexane.24comparison to that of sulphuric acid and the increased dissociation of chromic acid in dilute aqueous media.Ž.A more recent study of the solvent extraction of Ti IV from sulphuric acid by TOPO w x Ž.by Sato et al.36found that equilibrium was attained in 10min 15ml of each phase .The distribution coefficient increased sharply with increasing acid concentration.Tita-nium could be stripped from the organic phase using 1M NaOH.Titanium extraction was found to increase with increasing temperature in the temperature range of 10to 408C.These researchers demonstrated that sulphuric acid,present in the organic phase as Ž.the species H SO P TOPO,is displaced by the titanium complex.Infrared IR spectral 24interpretation showed that water-saturated TOPO contained the species TOPO P H O,2Ž.while in sulphuric acid solutions of high acidity,the species TOPO P OH SO was 3formed.Slope analysis demonstrated a second-power dependence of the distribution coefficient on the TOPO concentration.This stoichiometry of the extracted complex was w x w x supported by showing that the molar ratio TOPO :Ti approached a limiting value of 2.From analysis of the sulphate and water contents of the organic phase,it was furtherw x w 2y x w x w x shown that the molar ratio of Ti :SO :H O :TOPO s 1:2:1:2,indicating the stoi-42Ž.Ž.chiometry Ti H O SO P 2TOPO.From IR analysis it was found that titanium ex-242tracted into TOPO solution is bonded to the phosphoryl oxygen,suggesting that the w Ž.Ž.Ž.Ž.x extracted species exists as the complex Ti OH SO HSO TOPO in an octahedral 442arrangement.The following extraction reaction was proposed:q y Ti OH HSO q HSO q 2TOPO °TiO HSO P 2TOPO q H O.13Ž.Ž.Ž.244422Ž.w x Tri-n -butylphosphate TBP has been used by Sheng et al.37for the separation of aluminium,iron,and titanium chlorides.The solvent extraction separation of titanium from chloride medium is achieved using 30%TBP with 8%isodecanol as a phase Ž.modifier.Ti IV was readily stripped from the organic phase using 1to 2M HCl.Allal w x et al.38have reported the extraction of titanium from chloride media using mixtures of TBP,TOPO,and decanol.Under their conditions of study,titanium extraction in excess of 99%was achieved with equilibrium times of 3min.4.Treatment of titaniferous magnetitesThe typical iron:titanium:vanadium ratio in magnetites of the Bushveld Complex is approximately 150:20:1.Conventional roast–leach treatment of the ore would liberate most of the vanadium,but with limited dissolution of the iron and titanium.On the other hand,a direct sulphuric acid leach would be expected to dissolve all three elements of interest.The latter conditions would produce an iron-rich leach liquor of high ionic Ž.strength I f 2M .In such solutions,the extent of dissociation of ionic species is likely to be limited,and therefore iron,titanium,and vanadium are expected to be present,at least to some extent,as neutral species.This would indicate possible lack of selectivity in a solvent extraction system employing a neutral extractant.According to the speciation modelling results,the thermodynamically favoured titanium species are all hydroxides,even at low pH.The most prominent hydroxides,as well as the dominant sulphate species,are all cationic,suggesting that a cation exchanger,rather than a neutral solvating reagent,is expected to be preferred for the solvent extraction of titanium.Since extraction of vanadium is typically achieved at higher pH than that of titanium, it appears preferable to remove titanium from the leach solution prior to vanadium recovery to reduce neutralization costs.Under appropriate conditions,it would appear feasible to extract titanium using a cationic or neutral extractant,followed by vanadiumŽ.extraction using an anion exchanger.Iron III in sulphate media should not be extracted either by neutral or anionic extractants.However,interference from iron at the high concentrations found in the leach liquor is expected to occur.The species distribution of the leach liquor is of prime importance.Control of pH to prevent precipitation of iron species is also critical.Extraction from high acid solutions could be accompanied by competitive extraction of the acid itself or its anions.Solvent extraction recovery of vanadium from titaniferous magnetite sources could be successful if implemented subsequent to a roast–leach operation.In the case of direct leaching of titaniferous magnetites,however,it is likely that the presence of such large amounts of iron in solution would prevent a completely selective system from being achieved.Removal of iron prior to titanium and vanadium,for example,by solvent extraction or precipitation,is unlikely to present a cost-effective option,particularly as significant quantities of these elements would probably be co-extracted due to the relative ratios present in solution.These approaches have been tested on both laboratory and pilot-plant scales;thew xresults are reported independently39,40.5.ConclusionsTitanium can be extracted from acidic sulphate media using the commercially available reagents D2EHPA and TOPO.The main problems confronting the choice of a hydrometallurgical route for the recovery of titanium from the leach liquors of titanifer-ous magnetites are the lack of knowledge concerning the aqueous speciation of titanium and the myriad of species of various valencies that may be formed.Evidence has been presented for the existence of titanium cations,anions,and neutral species in acid media: the particular distribution of these,and of the analogous iron and vanadium species,will determine the efficiency with which a particular extractant system will perform.A further disadvantage of both reagents is the slow kinetics of extraction.This has been ascribed to the slow rate at which the–Ti–O–polymeric chains are broken down prior to being extracted as simple molecules or ions.Long residence times would be necessary to operate an economically viable solvent extraction operation.Also of significance for the use of TOPO as an extractant is the co-extraction of sulphuric acid, and consequent reduction in loading capacity under certain experimental conditions.Since most base metals exist in acidic sulphate media as cations,TOPO,as a neutral extractant,would appear to offer better selectivity for titanium than would D2EHPA.。
1. IDENTIFICATION OF THE SUBSTANCE/TREPARATION AND THE COMPANY/UNDERTAKING3.HAZARDS IDENTIFICATION4. FIRST AID MEASURESMATERIAL SAFETY DATA SHEETProduct name:Supplier:Tel:EMERGENCY OVERVIEW: May cause skin irritation and/or dermatitisPrinciple routes of exposure: Inhalation: Ingestion: Skin contact: Eye contact:SkinMay cause irritation of respiratory tract May be harmful if swallowed May cause allergic skin reaction Avoid contact with eyesStatements of hazard MAY CAUSE ALLERGIC SKIN REACTION.Statements of Spill of Leak Label Eliminate all ignition sources. Absorb and/or contain spill with inert materials (e.g., sand, vermiculite). Then place in appropriate container. For large spills, use water spray to disperse vapors, flush spill area. Prevent runoff from entering waterways or sewers.General advice:POSITION/INFORMATION ON INGREDIENTSInhalation:Skin contact:Ingestion:Eye contact:Protection of first – aiders:Medical conditions aggravated by exposure: In the case of accident or if you fell unwell, seek medical advice immediately (show the label where possible).Move to fresh air, call a physician immediately.Rinse immediately with plenty of water and seek medical adviceDo not induce vomiting without medical advice.In the case of contact with eyes, rinse immediately with plenty of water and seek medical advice.No information availableNone knownSuitable extinguishing media:Specific hazards:Special protective equipment for firefighters:Flash point:Autoignition temperature:NFPA rating Use dry chemical, CO2, water spray or “alcohol” foam Burning produces irritant fumes.As in any fire, wear self-contained breathing apparatus pressure-demand, MSHA/NIOSH (approved or equivalent) and full protective gearNot determinedNot determinedNFPA Health: 1 NFPA Flammability: 1 NFPA Reactivity: 0Personal precautions: Environmental precautions: Methods for cleaning up: Use personal protective equipment.Prevent product from entering drains.Sweep up and shovel into suitable containers for disposalStorage:7. 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TOXICOLOGICAL INFORMATIONConditions to avoid: Exposure to air or moisture over prolonged periods.Product information Acute toxicityChronic toxicity:Local effects: Chronic exposure may cause nausea and vomiting, higher exposure causes unconsciousness.Symptoms of overexposure may be headache, dizziness, tiredness, nausea and vomiting.Specific effects:May include moderate to severe erythema (redness) and moderate edema (raised skin), nausea, vomiting,headache.Primary irritation: Carcingenic effects: Mutagenic effects: Reproductive toxicity:No data is available on the product itself. No data is available on the product itself. No data is available on the product itself. No data is available on the product itself.Mobility:Bioaccumulation: Ecotoxicity effects: Aquatic toxicity:No data available No data available No data availableMay cause long-term adverse effects in the aquatic environment.12. ECOLOGICAL INFORMATION13. DISPOSAL CONSIDERATIONSWaste from residues/unused products:Contaminated packaging:Waste disposal must be in accordance with appropriate Federal, State and local regulations. This product, if unaltered by use, may be disposed of treatment at a permitted facility or as advised by your local hazardous waste regulatory authority. Residue from fires extinguished with this material may be hazardous.Do not re-use empty containers.UN/Id No:Not regulated14. TRANSPORT INFFORMATIONDOTProper shipping name: Not regulatedTGD(Canada)WHMIS hazard class: Non - controlledIMDG/IMOIMDG – Hazard Classifications Not ApplicableIMO – labels:15. REGULATORY INFOTMATION International Inventories16. 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●Vol.33,No 72015年7月中国资源综合利用China Resources Comprehensive Utilization铂钯精矿中的金、铂、钯含量较低,贱金属含量高,综合回收贵金属存在困难。
本研究针对铂钯精矿,选择电控除贱金属、富集贵金属,分别提取、精炼的生产工艺提取金、铂、钯。
实践表明,该工艺能有效回收金、铂、钯,且回收率高、生产成本低。
1试验部分1.1试验原料铂钯精矿在40℃下烘干4h ,其化学成分与含量见表1。
表1铂钯精矿的化学成分与含量1.2工艺原理1.2.1电控除杂采用盐酸酸浸铂钯精矿,同时通氯气控制电位,能有效地除去贱金属,其反应原理为:Cu+2HCl=CuCl 2+H 2↑(1)Zn+2HCl=ZnCl 2+H 2↑(2)Pb+2HCl=ZnCl 2+H 2↑(3)Bi+2HCl=BiCl 2+H 2↑(4)Se+4HCl=SeCl 4+2H 2↑(5)1.2.2大氯化溶解Au 、Pt 、Pd 经盐酸酸浸后渣,在盐酸、氯气作为氧化剂的条件下,酸浸渣中的金、铂、钯以氯金酸、氯铂酸、氯钯酸进入溶液。
其反应原理为:2Au+ClO 3-+6H ++7Cl -=2AuCl 4-+3H 20(6)3Pt+ClO 3-+6H ++11Cl -=3PtCl 4-+3H 20(7)3PtCl 4-+ClO 3-+5Cl -+6H +=3PtCl 4-+3H 20(8)3Pd+ClO 3-+6H ++11Cl -=3PdCl 4-+3H 20(9)3PdCl 4-+ClO 3-+5Cl -+6H +=3PdCl 4-+3H 20(10)1.2.3氯化铵沉铂钯将大氯化后液升温,在加入氧化剂、氯化铵的条件下,铂、钯以氯铂酸铵、氯钯酸铵的形式共沉下从铂钯精矿中提取金、铂、钯工艺研究王兴,崔家友,张善辉,陶明光(山东恒邦冶炼股份有限公司,山东烟台264109)摘要:针对在处理铜阳极泥过程中产生的铂钯精矿,采用电控除杂-大氯化溶解Au 、Pt 、Pd-氯化铵共沉铂钯-SO 2还原金-水煮分离铂钯-铂钯精炼工艺提取金、铂、钯。
实验室药材溶剂提取流程英文回答:Laboratory Solvent Extraction Process for Medicinal Plants.The solvent extraction process is a widely used technique in the pharmaceutical industry for extracting active compounds from medicinal plants. This process involves the use of solvents to dissolve and remove the desired compounds from the plant material. The choice of solvent is crucial as it should be able to selectively extract the target compounds while minimizing the extraction of unwanted impurities.Steps Involved in Solvent Extraction.The laboratory solvent extraction process typically involves the following steps:1. Sample Preparation: The plant material is dried, ground, and sieved to obtain a uniform particle size.2. Solvent Selection: The appropriate solvent is chosen based on the polarity and solubility of the target compounds.3. Extraction: The ground plant material is mixed with the selected solvent and agitated to facilitate the extraction process.4. Filtration: The mixture is filtered to separate the extracted solution from the plant solids.5. Concentration: The extracted solution is concentrated using rotary evaporation or freeze drying to remove the solvent.6. Purification: The concentrated extract may undergo further purification steps, such as column chromatography or recrystallization, to isolate the desired compounds.Factors Affecting Solvent Extraction.Several factors can affect the efficiency of the solvent extraction process, including:Solvent Polarity: Polar solvents are more effective at extracting polar compounds, while nonpolar solvents are better suited for nonpolar compounds.Temperature: Increasing the temperature can enhance the solubility of the target compounds and improve extraction efficiency.Extraction Time: Longer extraction times allow for greater extraction of the desired compounds.Solid-to-Solvent Ratio: The ratio of plant material to solvent can influence the extraction yield.Agitation: Agitation promotes better contact between the plant material and solvent, improving extraction efficiency.Applications of Solvent Extraction.Solvent extraction is a versatile technique used in the pharmaceutical industry for the following applications:Extraction of Active Ingredients: Solvent extraction is employed to isolate active compounds from medicinal plants for use in drug development and production.Standardization of Herbal Products: Solvent extraction allows for the standardization of herbal products by ensuring consistent levels of active ingredients.Quality Control: Solvent extraction is used to analyze and control the quality of herbal products by detecting the presence of specific compounds or impurities.中文回答:实验室药材溶剂提取流程。
绪论Strengthening basic researches on Chinese Medicinal Plants and its relations to realizing the modernization of CMM加强中国药用植物基础研究及其与中药现代化的关系Traditional Chinese Medicine(TCM)中药health care卫生健康Chinese traditional medicinal herbs中草药inciting side-effects明显的副作用go back to the nature回归自然the modernization of Chinese Materia Medica(CMM)中药现代化Surveys调查special projects专项调查scientific identification科学鉴定chemical constituents化学成分pharmacological experiments药理实验clinical applications临床适应性monographs各论、专论manuals手册Pharmacopoeia药典therapeutical efficacy疗效黄花蒿(Artemisia annua),青蒿(Artemisia apiacea)chloroquine resistant malaria/抗氯喹宁疟疾Pernicious(有害的)malaria/恶性疟疾cerebral(大脑的,脑的)malaria/脑疟疾derivatives/衍生物quinine/喹宁harringtonine三尖杉酯碱homoharringtonine高三尖杉酯碱extracted from提取leukemia白血病malignant lymphoma恶性淋巴瘤ginkgetin银杏黄酮criteria标准revise修正,校订systematic studies系统研究revising修订common-used Chinese materia medica常用中药材品种整理和质量研究impact n.冲击,碰撞era时代public health care公共健康事业traditional Chinese patent medicines and preparations中成药和中药制剂basic researches基础研究production生产marketing流通research研究①Identification of species/品种鉴定identifying鉴别clarifying澄清,阐明confused varieties易混淆的变种false matters伪品益胃生津,滋阴清热benefit the stomach,promote the production of body fluid and remove the excessive heat②Quality control and evaluation/质量的控制和评价intensive加强的,透彻的contents=components,constituentswith great care:小心翼翼地habitat:产地qualitative and quantitative analysis定性定量分析③The methods of research研究方法biotechnology生物技术molecular biology分子生物学remedy:n.药物,治疗法,赔偿,v.补救,矫正modern scientific methodologies现代科学方法①Strengthen the study of medicinal plant resources加强药用植物基源研究exploring new resources开发新的资源re-producting resources可持续性利用资源conservation of germplasm of the rare and endangered medicinal plants珍稀濒危药用植物的种质资源保护②Carry out the researches on specific biology of medicinal plantsspecific adj.种的,明确的,特殊的,具有特效的n.特效药,详情,特性③Map out GAP(Good Agriculturing Practice)in medicinal cultivationmap out规划seed quality standards种子的质量标准processing rules and regulations加工方法及规范④Established standards of quality control and renew methodologycriteria标准protocol草案foreign matter杂质⑤Apply modern comprehensive multidisciplinary studies on Chinese medicinal plants comprehensive:综合的,广泛的multidisciplinary:多学科⑥Establish information systems in modern research of Chinese medicinal herbsEthnobotany人类植物学Ethnopharmacology民族药理学Ethno-民族,种族semi-colonial and semi-feudal nation/半殖民半封建的国家constraint and devastation/压迫与毁坏the inheritance and development of Chinese troditional medicine……/继承和发扬many difficult and complicated diseases疑难杂症TERMINOLOGY部分要求的词汇中药Traditional Chinese Medicines中药材Chinese Materia Medica(CMM)Traditional Chinese Medicinal MaterialsChinese Crude Drugs中草药Traditional Chinese Medicinal HerbsChinese Herbal Medicines药用植物学Medicinal Plants民间药物Folklore Medicaments Folk Herbs Indigenous Drugs中成药Traditional Chinese Patent Medicines中药制剂Chinese Medicinal Preparations药用植物学Pharmaceutical Botany生药学Pharmacognosy药用植物分类学Pharmaceutical Plant Taxonomy植物化学Phytochemistry植物化学分类学Plant Chemotaxonomy药用植物志Flora of Medicinal Plants中药药剂学Traditional Chinese Pharmaceutics中药炮制学Science of Processing Chinese Crude Drugs显微生药学Microscopical Pharmacognosy本草学herbals药典pharmacopoeia细胞cell细胞壁cell wall初生壁primary wall次生壁secondary wall细胞核nucleus质体plastid叶绿体chloroplast染色体chromoplast纹孔pit结晶体crystal淀粉粒starch granule(grain)脐点hilum(pi.hila)层纹striation单粒single starch granule复粒compound starch granule半复粒semi-compound starch granule 蛋白质protein脂类化合物lipid挥发油volatile oil苷glycoside 生物碱alkaloid皂苷saponin萜terpene三萜皂苷triterpenoid黄铜flavonoid蒽醌anthraquinone酚phenol香豆素coumarin鞣质rannin氨基酸amino acid菊糖inulin草酸钙结晶calcium cxalate crystal 簇晶clusrer crystal(cluster,druse)针晶acicular crystal(needle) Parenchyma薄壁组织Parenchymatous cell包庇细胞Epidermal tissue表皮组织Epidermis表皮Cuticle角质层stoma(pl.stomata)气孔guard cell保卫细胞subsidiary cell副卫细胞非腺毛non-glandular hair腺毛glandular hair腺鳞glandular scale周皮periderm木栓层cork木栓形成层cork cambium(phellogen)栓内层phelloderm皮层cortex皮孔lenticel形成层cambium次生木质部secondary xylem次生韧皮部secondary phloem分泌组织secretory tissue树脂道resin canal厚角组织collenchyma纤维fibre(fiber)韧皮纤维phloem fibre木纤维xylem fibre晶鞘纤维crystal fibre层纹striation木化lignified增厚thickening增厚细胞壁thickened wall 导管vessel网纹导管reticulated vessel具缘纹孔导管bordered pitted vessel 筛管sieve tube维管束vascular bundle外韧维管束collateral bundle异性维管束abnormal vascular bundle 形成层成环cambium ring主根main(tap)root定根normal root须根fibrous root不定根adventitious root细根rootler初生构造primary structure次生构造secondary structure皮层cortex中柱鞘pericycle初生木质部primary xylem髓部pith射线ray木栓层cork植物phyta科aceae丹参Pubescent软毛Stem4-angled茎4棱Angled棱Leaves opposite叶对生Verticillate轮生pseudo-假的Racemes总状花序stamens雄蕊Gynobasic着生于基部的Nutlets坚果Ellipsoid椭圆形Vermillion朱红色serrate锯齿状的Retuse浅凹形Falcate钩状的Filament花丝Style花柱Anther花粉囊fragile:脆的astringent:收敛性的ferric chloride:三氯化铁TS:test solutiondull:暗的cortex:栓皮,皮层phelloderm:栓内层a stoppered test tube:具塞试管stand for:静置residue:残渣reference drug:对照药材CRS:Chemical Reference Standard养心安神:clear heart-fire and remove restlessnessRhizomes short and stout,sometimes with remains of a stem at the apex.根茎短而粗壮,Externally brownish-red or dark brownish-red,rough,longitudinally wrinkled.dissolved on mounting in chloral hydrate solution.Boil5g of the powder in50ml of water for15~20minutes,cool and filter.Concentrate the filtrate on a water bath,dissolve the extract in3~5ml of ethanol,filter.Apply several drops of the filtrate to a piece of filter paper,allow it to dry and examine under ultra-violet light(365nm), a bright bluish-grey fluorescence is produced.Expose the filter paper to ammonia vapour for20 minutes,remove the filter paper and examine again under ultra-violet light(365nm),a pale bluish-green fluorescence is produced.置5g粉末于50ml水中煎煮15~20分钟,冷却后过滤.在水浴中浓缩滤液,用3~5ml乙醇溶解浓缩产物,过滤。
有机化学专业英语中英文对照第一章无机化学英文命名1.1元素的英文命名S-block ElementIAH Hydrogen Li Lithium Na Sodium K PotassiumRb Rubidium Cs Cesium Fr FranciumIIABe Beryllium Mg Magnesium Ca Calcium Sr Strontium Ba Barium Ra RadiumP-block ElementIIIA IV A V AB BoronC Carbon N NitrogenAl Aluminium Si Silicon P PhosphorusGa Gallium Ge Germanium As ArsenicIn Indium Sn Tin Sb AntimonyTl Thallium Pb Lead Bi BismuthVIA VIIA0He Helium O Oxygen F Fluorine Ne NeonS Sulfur Cl Chlorine Ar ArgonSe Selenium Br Bromine Kr KryptonTe Tellurium I Iodine Xe XenonPo Polonium At Astatine Rn RadonCommon Transition ElememtFe:iron Mn:manganese Cu:copper Zn:zincHg:mercury Ag:silver Au:gold1.2离子、氧化物、酸、碱、盐及其他化合物的英文命名Na+Sodium Al3+AluminumK+Potassium Ca2+CalciumFe2+Iron(II)or FerrousFe3+Iron(III)or FerricCr2+Chromium(II)Cr3+Chromium(III)Mn4+Manganese(IV)Mn2+Manganese(II)FeO:iron(II)oxide或ferrous oxideFe2O3:iron(III)oxide或ferric oxideCu2O:copper(I)oxide或cuprous oxideCuO:copper(II)oxide或cupric oxideCl-Chloride O=OxideBr-Bromide OH-HydroxideI-Iodide CN-CyanideS=Sulfide H-Hydride HF hydrogen fluoride HCl hydrogen chloride HBr hydrogen bromide HI hydrogen iodideH2S hydrogen sulfide H2Se hydrogen selenideH2Te hydrogen telluridePH3:phosphine或phosphane AsH3:arsine或arsaneSbH3:stibine或stibane BiH3:bismuthaneCH4:methane SiH4:silaneB2H6:diboraneHCl:hydrochloric acidH2S:hydrosulfuric acidAl(OH)3Aluminum hydroxideNaOH Sodium hydroxideCa(OH)2Calcium hydroxideBa(OH)2Barium hydroxideCo(OH)2Cobalt(II)hydroxideHgSO4Mercury(II)sulfateHg2SO4Mercury(I)sulfateKNO3Potassium nitrateNa2CO3Sodium carbonateNaClO Sodium hypochloriteFeSO4iron(II)sulfateKMnO4potassium permanganateNaHSO4Sodium hydrogen sulfateNa2HPO4Disodium hydrogen phosphateNaH2PO4Sodium dihydrogen phosphateCa(HSO4)2Calcium bisulfateNaHCO3Sodium hydrogencarbonate或Sodium bicarbonateAlCl3·6H2O:aluminum chloride6-water或aluminum chloride hexahydrateAlK(SO4)2·12H2O:aluminium potassium sulfate12-waterH2CO3Carbonic acidH2SO4Sulfuric acidH3PO4Phosphoric acidHNO3Nitric acidHClO4Perchloric acidHCl Hydrochloric acidH2SO3Sulfurous acidH3PO3Phosphorous acidHNO2Nitrous acidHClO Hypochlorous acidHClO2Chlorous acidNaming coordination complexLigandsCN-Cyano NO2-NitroF-Fluoro NO3-NitratoCl-Chloro CO3=CarbonatoBr-Bromo CH3COO-AcetatoO=Oxo H-HydridoOH-Hydroxo-O2CCO2-Oxalato1.3配位化学中常见配体的名称1.4常用无机化学专业英语词汇相对原子质量relative atomic mass消去反应elimination reaction硝化反应nitratlon reaction硝酸钡barium nitrate硝酸银silver nitrate溴的四氯化碳溶液solution of bromine in carbon tetrachloride溴化钠sodium bromide溴水bromine water溴水bromine water盐类的水解hydrolysis of salts盐析salting-out焰色反应flame test氧化剂oxidizing agent氧化铝aluminium oxide氧化铁iron(III)oxide 乙醇ethanol乙醛ethana1乙炔ethyne乙酸ethanoic acid乙酸乙酯ethyl acetate乙烯ethene银镜反应silver mirror reaction硬脂酸stearic acid油脂oils and fats有机化合物organic compound元素周期表periodic table of elements 元素周期律periodic law of elements 原电池primary battery原子序数atomic number皂化反应saponification粘合剂adhesive蔗糖sucrose指示剂Indicator酯ester酯化反应esterification周期period族group(主族:main group)Bunsen burner本生灯product化学反应产物flask烧瓶apparatus设备PH indicator PH值指示剂,氢离子(浓度的)负指数指示剂matrass卵形瓶litmus石蕊litmus paper石蕊试纸graduate,graduated flask量筒,量杯reagent试剂test tube试管burette滴定管retort曲颈甑still蒸馏釜cupel烤钵crucible pot,melting pot坩埚pipette吸液管filter滤管stirring rod搅拌棒element元素body物体compound化合物atom原子gram atom克原子atomic weight原子量atomic number原子数atomic mass原子质量molecule分子electrolyte电解质ion离子anion阴离子cation阳离子electron电子isotope同位素isomer同分异物现象polymer聚合物symbol复合radical基structural formula分子式valence,valency价monovalent单价bivalent二价halogen成盐元素bond原子的聚合mixture混合combination合成作用compound合成物alloy合金organic chemistry有机化学inorganic chemistry无机化学derivative衍生物series系列acid酸hydrochloric acid盐酸sulphuric acid硫酸nitric acid硝酸aqua fortis王水fatty acid脂肪酸organic acid有机酸hydrosulphuric acid 氢硫酸hydrogen sulfide氢化硫alkali碱,强碱ammonia氨base碱hydrate水合物hydroxide氢氧化物,羟化物hydracid氢酸hydrocarbon碳氢化合物,羟anhydride酐alkaloid生物碱aldehyde醛oxide氧化物phosphate磷酸盐acetate醋酸盐methane甲烷,沼气butane丁烷salt盐potassium carbonate碳酸钾soda苏打sodium carbonate碳酸钠caustic potash苛性钾caustic soda苛性钠ester酯gel凝胶体analysis分解fractionation分馏endothermic reaction吸热反应exothermic reaction放热反应precipitation沉淀to precipitate沉淀to distil,to distill蒸馏distillation蒸馏to calcine煅烧to oxidize氧化alkalinization碱化to oxygenate,to oxidize脱氧,氧化to neutralize中和to hydrogenate氢化to hydrate水合,水化to dehydrate脱水fermentation发酵solution溶解combustion燃烧fusion,melting熔解alkalinity碱性isomerism,isomery同分异物现象hydrolysis水解electrolysis电解electrode电极anode阳极,正极cathode阴极,负极catalyst催化剂catalysis催化作用oxidization,oxidation氧化reducer还原剂dissolution分解synthesis合成reversible可逆的摩尔mole摩尔质量molar mass品红magenta或fuchsine葡萄糖glucose气体摩尔体积molar volume of gas 铅蓄电池lead storage battery强电解质strong electrolyte氢氟酸hydrogen chloride氢氧化铝aluminium hydroxide取代反应substitution reaction醛aldehyde炔烃alkyne燃料电池fuel cell弱电解质weak electrolyte石油Petroleum水解反应hydrolysis reaction四氯化碳carbon tetrachloride塑料plastic塑料的降解plastic degradation塑料的老化plastic ageing酸碱中和滴定acid-base neutralization titration酸雨acid rain羧酸carboxylic acid碳酸钠sodium carbonate碳酸氢铵ammonium bicarbonate碳酸氢钠sodium bicarbonate糖类carbohydrate烃hydrocarbon烃的衍生物derivative of hydrocarbon烃基hydrocarbonyl同分异构体isomer同素异形体allotrope同位素isotope同系物homo1og涂料coating烷烃alkane物质的量amount of substance物质的量浓度amount-of-substance concentration of B烯烃alkene洗涤剂detergent纤维素cellulose相对分子质量relative molecular mass 极性键polar bond加成反应addition reaction加聚反应addition polymerization甲烷methane碱金属alkali metal碱石灰soda lime结构式structural formula聚合反应po1ymerization可逆反应reversible reaction空气污染指数air pollution index勒夏特列原理Le Chatelier's principle离子反应ionic reaction离子方程式ionic equation离子键ionic bond锂电池lithium cell两性氢氧化物amphoteric hydroxide两性氧化物amphoteric oxide裂化cracking裂解pyrolysis硫氰化钾potassium thiocyanate硫酸钠sodium sulphide氯化铵ammonium chloride氯化钡barium chloride氯化钾potassium chloride氯化铝aluminium chloride氯化镁magnesium chloride氯化氢hydrogen chloride氯化铁iron(III)chloride氯水chlorine water麦芽糖maltose煤coal酶enzyme二氧化氮nitrogen dioxide二氧化硅silicon dioxide二氧化硫sulphur dioxide二氧化锰manganese dioxide芳香烃arene放热反应exothermic reaction非极性分子non-polar molecule非极性键non-polar bond肥皂soap分馏fractional distillation酚phenol复合材料composite干电池dry cell干馏dry distillation甘油glycerol高分子化合物polymer共价键covalent bond官能团functional group光化学烟雾photochemical fog过氧化氢hydrogen peroxide合成材料synthetic material合成纤维synthetic fiber合成橡胶synthetic rubber核电荷数nuclear charge number核素nuclide化学电源chemical power source化学反应速率chemical reaction rate氨ammonia氨基酸amino acid铵盐ammonium salt饱和链烃saturated aliphatic hydrocarbon苯benzene变性denaturation不饱和烃unsaturated hydrocarbon超导材料superconductive material臭氧ozone醇alcohol次氯酸钾potassium hypochlorite醋酸钠sodium acetate蛋白质protein氮族元素nitrogen group element碘化钾potassium iodide碘化钠sodium iodide电化学腐蚀electrochemical corrosion电解质electrolyte电离平衡ionization equilibrium电子云electron cloud淀粉starch淀粉碘化钾试纸starch potassium iodide paper化学键chemical bond化学平衡chemical equilibrium 还原剂reducing agent磺化反应sulfonation reaction霍尔槽Hull Cell极性分子polar molecule 2.5常用无机元素英文Actinium(Ac)锕Aluminium(Al)铝Americium(Am)镅Antimony(Sb)锑Argon(Ar)氩Arsenic(As)砷Astatine(At)砹Barium(Ba)钡Berkelium(Bk)锫Beryllium(Be)铍Bismuth(Bi)铋Boron(B)硼Bromine(Br)溴Cadmium(Cd)镉Caesium(Cs)铯Calcium(Ca)钙Californium(Cf)锎Carbon(C)碳Cerium(Ce)铈Chlorine(Cl)氯Chromium(Cr)铬Cobalt(Co)钴Copper(Cu)铜Curium(Cm)锔Dysprosium(Dy)镝Einsteinium(Es)锿Erbium(Er)铒Europium(Eu)铕Fermium(Fm)镄Fluorine(F)氟Francium(Fr)钫Gadolinium(Gd)钆Gallium(Ga)镓Germanium(Ge)锗Gold(Au)金Hafnium(Hf)铪Helium(He)氦Holmium(Ho)钬Hydrogen(H)氢Indium(In)铟Iodine(I)碘Iridium(Ir)铱Iron(Fe)铁Krypton(Kr)氪Lanthanum(La)镧Lawrencium(Lr)铹Lead(Pb)铅Lithium(Li)锂Lutetium(Lu)镥Magnesium(Mg)镁Manganese(Mn)锰Mendelevium(Md)钔Mercury(Hg)汞Molybdenum(Mo)钼Neodymium(Nd)钕Neon(Ne)氖Neptunium(Np)镎Nickel(Ni)镍Niobium(Nb)铌Nitrogen(N)氮Nobelium(No)锘Osmium(Os)锇Oxygen(O)氧Palladium(Pd)钯Phosphorus(P)磷Platinum(Pt)铂Plutonium(Pu)钚Polonium(Po)钋Potassium(K)钾Praseodymium(Pr)镨Promethium(Pm)钷Protactinium(Pa)镤Radium(Ra)镭Radon(Rn)氡Rhenium(Re)铼Rhodium(Rh)铑Rubidium(Rb)铷Ruthenium(Ru)钌Samarium(Sm)钐Scandium(Sc)钪Selenium(Se)硒Silicon(Si)硅Silver(Ag)银Sodium(Na)钠Strontium(Sr)锶Sulphur(S)锍Tantalum(Ta)钽Technetium(Tc)锝Tellurium(Te)碲Terbium(Tb)铽Thallium(Tl)铊Thorium(Th)钍Tin(Sn)锡Thulium(Tm)铥Titanium(Ti)钛Tungsten(W)钨Uranium(U)铀Vanadium(V)钒Xenon(Xe)氙Ytterbium(Yb)镱Yttrium(Y)钇Zinc(Zn)锌Zirconium(Zr)锆第二章有机化学英文命名2.1有机化学系统命名中主要官能团的优先顺序1.鎓盐(onium and similar cations)2.酸(acids):按COOH、(C)OOH次序,然后是它们的S和Se的衍生物,再次为磺酸、亚磺酸等。
Extraction of palladium (II)from nitric acid medium byimidazolium nitrate immobilized resinK.A.Venkatesan,B.Robert Selvan,M.P.Antony,T.G.Srinivasan ⁎,P.R.Vasudeva RaoFuel Chemistry Division,Chemical Group,Indira Gandhi Centre For Atomic Research,Kalpakkam 603102,IndiaReceived 31July 2006;received in revised form 20November 2006;accepted 21November 2006Available online 26January 2007AbstractImidazolium nitrate functional groups (Im –NO 3)were anchored onto a polystyrene –divinylbenzene resin matrix,and investigated for the extraction of palladium (II)from nitric acid medium.The rate of extraction and distribution coefficient,K d ,mL/g,of palladium (II)were measured as a function of extent of functionalization,and concentrations of nitric acid,sodium nitrate and palladium nitrate.K d values of palladium (II)show a maximum in 3.0M –4.0M nitric acid.Slope analysis of the distribution data obtained at various aqueous phase nitrate concentrations and resin phase exchanging capacity suggest the involvement of anion exchange mechanism for the extraction of palladium (II)from nitric acid medium.The ion exchange isotherm was fitted using Langmuir adsorption model and the apparent ion exchange capacity (b =88mg/g)was determined.The performance of the resin under dynamic conditions was evaluated by following a breakthrough curve and the data was fitted using Thomas model.©2006Elsevier B.V .All rights reserved.Keywords:Ion exchange;Anchoring;Fission palladium;Imidazolium nitrate resin;Langmuir adsorption1.IntroductionThe concept of by-product utilization arising from nuclear industry evolved in the 1950s.Potentially useful and strategic by-products are produced during fission of fissile elements (Ache et al.,1989,1993).The PUREX process (Swanson,1984)aims to recover strategic ele-ments leaving a raffinate containing all the other fission products in 3–4M nitric acid medium.The long-lived radioactive elements such as 137Cs (t 1/2=30.1a)and 90Sr (t 1/2=28.5a)in addition to some non-radioactive platinum group metals are produced,in significant quantities,as by-products of fission (Ache et al.,1989,1993).These were regarded as wastes a few decades agobut are now being targeted for recovery,owing to the upsurge in the utilization of these radioisotopes in the area of medicine (Brans et al.,2006;Woo and Sandford,2002),food irradiation (Diehl,2002;Lacroix and Ouat-tara,2000;Sivinski,1983)and sewage treatment (Bor-rely et al.,1998).Furthermore,the potential application of platinum group metals in various industries is well-established (Ache et al.,1989;Jenson et al.,1984,1980;Kolarik and Renard,2005).Most of the fission palladium isotopes in the spent nuclear fuel are non-radioactive or very weakly radio-active.It comprises of stable isotopes 104Pd (17wt.%),105Pd (29wt.%)106Pd (21wt.%)108Pd (12wt.%)110Pd (4wt.%)and a radioactive 107Pd (17wt.%)isotope,which has a half-life of 6.5×106y.The intrinsic radio-activity of 107Pd (soft β-emittor with E max of 35keV)is very weak and it can be tolerated for manyindustrialHydrometallurgy 86(2007)221–229/locate/hydromet⁎Corresponding author.Fax:+914427480065.E-mail address:tgs@.in (T.G.Srinivasan).0304-386X/$-see front matter ©2006Elsevier B.V .All rights reserved.doi:10.1016/j.hydromet.2006.11.006applications(Kolarik and Renard,2005).Thus the sepa-ration of palladium from high level liquid waste (HLLW)may provide considerable incentives in view of its widespread applications in various chemical, pharmaceutical and electronic industries(Ache et al., 1989;Jenson et al.,1984,1980;Kolarik and Renard, 2005).In addition,isolation of palladium from HLLW may indirectly solve some of the problems associated with the management of high level radioactive waste described elsewhere(Sundaram and Perez,2000). Therefore,removal of PGM from HLLW is desirable before immobilization to eliminate complex problems during vitrification and also to improve the quality of final waste form.The composition of HLLW is de-scribed elsewhere(Mathur et al.,1996)and majority of the elements present in HLLW exist as cationic species in3–4M nitric acid medium.However,palladium(II)in HLLW exists in the form of anionic nitrate complexes (Kolarik and Renard,2003a).Recovery of valuable PGMs from HLLW has been extensively studied in the last two decades(Ache et al., 1989;Jenson et al.,1984,1980;Rizvi et al.,1996; Shukla et al.,1993;Mimura et al.,2001;Lee and Chung, 2000;Koizumi et al.,1993;Mezhov et al.,2002a,b) with particular interest in the separation of palladium.A recent review by Kolarik and Renard(2003a,b,2005) details the methods and materials reported to date for the recovery of valuable PGM from spent nuclear fuel and the behavior of fission PGM in HLLW.Recently we have also investigated the separation and recovery of palladium by an electrorefining method using room temperature ionic liquids(Giridhar et al.,2006a),solid phase extraction by sulphur based resins(Venkatesan et al.,2005)and solvent extraction by ylides(Mohan Raj et al.,2006)and Aliquat-336(Giridhar et al., 2006b).A new method of extraction-cum-electrodepo-sition has been developed for the recovery of palladium from nitric acid medium(Giridhar et al.,2006b).Since the target metal,palladium(II)is a soft acid,selective extraction of it is feasible with soft base extractants containing S and N as ligands or donors.Various organo-functionalized resins are also studied for the extraction of palladium and other precious metals from non-radioactive feed solution(Jermakowicz-Bartko-wiak et al.,2005;Kaledkowski and Trochimczuk, 2006;Sanchez et al.,2004;Qu et al.,2006).Sulphur based extractants and resin are reported to exhibit extraordinary selectivity for palladium at all nitric acid concentrations(Rizvi et al.,1996;Shukla et al.,1993; Mimura et al.,2001);however,they are vulnerable to acid-degradation.Several conventional anion exchange resins(Kolarik and Renard,2003a;El-Said et al.,2002;Pokhitonov and Romanovskii,2005;Korolev et al., 2005)containing tertiary and quaternary ammonium ions as functional groups were also reported for the separation of palladium.However,these conventional exchangers exhibit poor selectivity for palladium from nitric acid feed representing HLLW,and usually operate at higher temperatures for increasing the selectivity. Anion resin functionalized with N,N-dimethylbenzimi-dazole(AR-01)was reported(Lee and Chung,2000; Kolarik and Renard,2003a)to extract palladium from 6M nitric acid medium and attains equilibrium after 20h at60°C.However,methylimidazole anchored on polystyrene–divinylbenzene copolymer has not been studied for the extraction of palladium from nitric medium.Therefore,the objective of the present paper is to anchor1-methylimidazole on chloromethylated resin and to study the extraction behavior of palladium(II) from nitric acid medium on it.The effects of various parameters such as time,concentration of nitric acid and palladium ion on the extraction of palladium by the resin is reported.Extraction of palladium under dynamic conditions is also reported.2.Experimental2.1.MaterialsAll the reagents used in the present study were of analytical reagent grade.Chloromethylated polysty-rene–divinylbenzene(4.5mmol/g;4%cross linkage) copolymer was purchased from M/s.Thermax(India) Pvt.Ltd.,Pune,India.The chloromethylated resin was washed with methanol and acetone to remove mono-mers and dried in air.1-methylimidazole was procured from Lancaster UK.Palladium(II)nitrate was procured from M/s.Otto Chemie.,Mumbai.2.2.Preparation of imidazolium nitrate anchored resin (Im–NO3)The reaction scheme adopted for the preparation of Im–NO3is shown below in Scheme1.It involves the immersion of chloromethylated resin(2g=9mmol)in a round bottomed flask containing50mL of toluene and desired amount of1-methylimidazole.The entire mixture was refluxed for the desired interval of time.The su-pernatant was then decanted,and the product was washed with toluene,methanol and acetone and dried in air.The amount of methylimidazole anchored on the resin was estimated by eluting the chloride ion present in the resin.Sodium nitrate solution(0.1M,100mL)was passed into a column packed with0.5g of the anchored resin.The222K.A.Venkatesan et al./Hydrometallurgy86(2007)221–229effluent and water washings were collected in a 250mL standard flask and the chloride content in the solution was measured by Mohr's method.The entire quantity of resin was converted to nitrate form by passing sodium nitrate solution in to a column packed with the resin until the effluent is free from chloride ion (tested with acidified silver nitrate).This nitrate form of imidazolium anchored resin,Im –NO 3,was used for the entire study.2.3.Effect of nitric acidAll the experiments were carried out at 298K.Extraction of palladium as a function of nitric acid concentration was studied by equilibrating resin with solution containing 6.2×10−4M palladium ion present in desired concentration of nitric acid.After 6h of equilibration,an aliquot was taken from the supernatant.The concentration of palladium present in the aliquot before and after equilibration was measured by spec-trophotometric procedure (Rizvi and Natrajan,1990)using Arsenazo III as coloring agent at the λmax of 627nm.The distribution coefficient (K d ,mL/g)and the percentage of palladium extracted by the resin were calculated using Eqs.(1)and (2)respectively.K d ¼½Pd ini −½Pd fin ½Pd finV mð1Þ%Extraction ¼1−½Pd fin ½Pd ini100ð2Þwhere V and m are respectively the volume of the so-lution and mass of the sorbent taken for equilibration.The kinetics of extraction were determined by sam-pling the above solutions at various times.2.4.Effect of [NO 3−]The effect of nitrate ion concentration on the ex-traction of palladium was studied by equilibrating 0.05g of Im –NO 3resin with aqueous solution containing 6.2×10−4M palladium nitrate,1.0M nitric acid,and desired concentration of sodium nitrate.The total nitrate ion concentration in the test solution was varied from 1.0M to 5.0M by varying the concentrations of nitric acid and sodium nitrate.The distribution ratio of palladium was measured as described above.Similar experiments were performed with the concentration of nitric acid in the test solution 3.0M (or)5.0M and the total nitrate ion concentration up to 6.0M.2.5.Effect of [Im –NO 3]The influence of concentration of exchanging nit-rate in the resin on the distribution coefficient of pal-ladium was studied by equilibrating the Im –NO 3resin with aqueous solution containing 6.2×10−4M palla-dium nitrate dissolved in desired concentration of nitric acid.The nitrate exchange capacity was changed dur-ing preparation by using substoichiometric amounts of 1-methylimidazole.Palladium present in aqueous phase before and after extraction was determined as described above and the distribution values were calculated.2.6.Effect of [Pd(II)]The extraction isotherm of palladium was constructed from the results of the experiments that involved equilibration of 0.05g of the resin with aqueous phase containing desired concentration of nitric acid (3.0M)and palladium nitrate(10−4–10−2M)The concentration of Pd(II)present in the aqueous phase before and after extraction was measured and the concentration of Pd(II)in resin phase was calculated.2.7.Column studyThe performance of the sorbent under dynamic con-dition was assessed by column breakthrough experi-ments.In this experiment 1.0g (=2mL bed volume)of Im –NO 3was immersed in water and loaded into a glass column of radius 0.25cm.The sorbent bed waswashedScheme 1.Synthesis of imidazole anchored resin I=Chloromethylated resin;II=1-methylimidazole;III =Imidazole anchored resin —Cl form;Im –NO 3=Imidazole anchored resin —NO 3form.223K.A.Venkatesan et al./Hydrometallurgy 86(2007)221–229with nitric acid of concentration equivalent to that of feed.The experimental feed solution containing 6.2×10−4M palladium ion diluted in 3.0M nitric acid was passed at a flow rate of 0.5mL/min.The effluent was collected at various intervals of time and analyzed for palladium.The ratio of the concentration of palladium in the effluent (C )to that of feed (C o )was plotted against the bed volume of the solution passed through the bed to obtain the breakthrough curve.3.Results and discussion 3.1.Preparation of Im –NO 3The results of ion exchange capacity obtained for anchoring of 1-methylimidazole on chloromethylated resin are shown in Table 1.When the mole ratio of chloromethylated resin to 1-methylimidazole is 1:10,rapid functionalization of methylimidazole is observed,leading to the exchange capacity of 3.5mmol/g within 40min of refluxing.Subsequently,the rate of functionalization is slow and a capacity of 4mmol/g is achieved after 5h of refluxing.Lowering of 1-methylimidazole concentration in the mixture (to 1:1.5)does not have much impact on the capacity values.Therefore,bulk of the resin (Im –NO 3)with capacity of 4mmol/g was prepared by refluxing 10g of chloromethylated resin (4.5mmol/g)with 1-methyli-midazole (68mmol)in 150mL of toluene for 5h.3.2.Kinetics of extractionThe rate of uptake of palladium by Im –NO 3from nitric acid medium is shown in Fig.1.At all nitric acid concentrations,rapid extraction of palladium is ob-served in the initial stages of equilibration followed by the establishment of equilibrium occurring within 200min of equilibration.The rate of uptake of palla-dium (d[Pd]t /d t )by Im –NO 3is given by Eq.(3).d ½Pd td t¼k 1½Resin ð3Þwhere k 1is the first order rate constant and [Resin]is the residual concentration of extraction sites in the resin phase,which can be related to the concentration of palladium in the resin phase at various intervals of time by Eq.(4).½Resin ¼½Pd eqm −½Pd tð4Þwhere [Pd]eqm and [Pd]t are the palladium loading at equilibrium and at various intervals of time respectively.Substituting Eq.(4)in Eq.(1)gives d ½Pd t½Pd eqm −½Pd t¼k 1d tð5ÞIntegration of Eq.(5)between the limits,at t =0,[Pd]t =0and at t =t ,[Pd]t =[Pd]t ,results in Eq.(6),which is known as Lagergren equation ½Pd t ¼½Pd eqm ð1−e −k 1t Þð6ÞNon-linear regression of the kinetic data using Eq.(6)is also shown in Fig.1and the rate constant (k 1)obtained from the fitting increased from 5.9×10−2min −1to 7.4×10−2min −1when the concentration of nitric acid increased from 2.0M to 4.0M.3.3.Effect of [HNO 3]The distribution coefficient of palladium (II)as a function of nitric acid concentration on Im –NO 3isTable 1Variation of ion exchange capacity of Im –NO 3as a function of duration of refluxing and ratio of chloromethylated resin to 1-methylimidazole taken for synthesis Mole ratio of resin:1-methylimidazole Duration of refluxing (min)Ion exchange capacity,mmol/g 1:1040 3.561:1060 3.591:10120 3.601:10180 3.701:10300 3.991:10480 4.001:5300 3.981:1.5300 4.061:160 3.431:0.7560 3.011:0.5602.80Fig.1.Kinetics of extraction of palladium (II)by Im –NO 3.V /m =50mL/g;T =298K;[Pd(II)]=6.2×104M.224K.A.Venkatesan et al./Hydrometallurgy 86(2007)221–229shown in Fig.2.It is seen that K d values increases withincrease in the concentration of nitric acid reaching a maximum value at 3.0M nitric acid which is ideally suited for the extraction of palladium from nitric acid medium representing high level nuclear wastes.It should be noted that the distribution coefficients obtained in the case of Im –NO 3resin are 3–4times higher than the values obtained for Dowex 1×4resin (quaternary ammonium salt with nitrate exchanging ion)under similar conditions.The reason for high distribution coefficients obtained for Im –NO 3is not clear,however it could be due to the strong interaction of anionic palladium nitrate species with the imidazolium resin.The distribution trend observed in the present study indicates that palladium (II)may be forming a series of anionic complexes with nitrate ions in aqueous solution,which are likely to be extracted by Im –NO 3through anion exchange.The formation of various nitrate complexes of palladium (II)from free palladium (II)ion ([Pd(H 2O)4]2+)are given below,where βn are the corresponding formation constants.½Pd ðH 2O Þ4 2þþNO −3()½Pd ðH 2O Þ3ðNO 3Þ þb 1¼½Pd ðH 2O Þ3ðNO 3Þþ½Pd ðH 2O Þ4 2þ½NO −3ð7Þ½Pd ðH 2O Þ4 2þþ2NO −3()½Pd ðH 2O Þ2ðNO 3Þ2 b 2¼½Pd ðH 2O Þ2ðNO 3Þ2 ½Pd ðH 2O Þ4 2þ½NO −3 2ð8Þ½Pd ðH 2O Þ4 2þþ3NO −3()½Pd ðH 2O ÞðNO 3Þ3 −b 3¼½Pd ðH 2O ÞðNO 3Þ3½Pd ðH 2O Þ4 ½NO 3ð9Þ"½Pd ðH 2O Þ4 2þþ4NO −3()Pd ðNO 3Þ2−4b 4¼½Pd ðNO 3Þ4 2−½Pd ðH 2O Þ4 2þ½NO −34ð10ÞThe total concentration of palladium (C Pd )is given by Eq.(11).C Pd ¼½Pd ðH 2O Þ4 2þþ½Pd ðH 2O Þ3ðNO 3Þ þþ½Pd ðH 2O Þ2ðNO 3Þ2þ½Pd ðH 2O ÞðNO 3Þ3 −þ½Pd ðNO 3Þ4 2Àð11ÞUsing Eqs.(7)–(10),the total concentration of palla-dium,C Pd ,and the concentration of [Pd(H 2O)(NO 3)3]−can be written as C Pd ¼½Pd ðH 2O Þ4 f 1þX 4i ¼1b i ½NO −3 igð12Þ½Pd ðH 2O ÞðNO 3Þ3 −¼b 3½NO −3 3C Pd1þP 4i ¼1b i ½NO −3ið13ÞIf the mechanism of extraction involves the ionexchange of [Pd(H 2O)(NO 3)3]−species as shown in Eq.(14),then the equilibrium constant (K )of extraction and the distribution coefficient (K d )of palladium can be represented by Eqs.(15)and (16)respectively.Im ÀNO 3þ½Pd ðH 2O ÞðNO 3Þ3 −()Im À½Pd ðH 2O ÞðNO 3Þ3 þNO −3ð14ÞK ¼½Im ÀPd ðH 2O ÞðNO 3Þ3 ½NO −3 ½Im ÀNO 3 ½Pd ðH 2O ÞðNO 3Þ3 −ð15ÞK d ¼½Im ÀPd ðH 2O ÞðNO 3Þ3C Pdð16ÞSubstituting the value of [Pd(H 2O)(NO 3)3]−fromEq.(13),and combining Eqs.(15)and (16)results inK d ¼K ½Im ÀNO 3 b 3½NO −3 21þP 4i ¼1b i ½NO −3i ð17ÞAt low nitrate ion concentrations,1NNX 4i ¼1b i ½NO −3ið18ÞFig.2.Variation of distribution coefficient of palladium (II)with concentration of nitric acid.Equilibration time =6h;T =298K;[Pd(II)]=6.2×10−4M.225K.A.Venkatesan et al./Hydrometallurgy 86(2007)221–229and Eq.(17)can be simplified to Eq.(19),where the distribution coefficient (K d )of palladium (II)variesdirectly with [NO 3−]2.K d ∝K ½Im ÀNO 3 ½NO −32ð19ÞAt high nitrate ion concentrations,the denominator term tends towards the fourth power of nitrate ion concentration as shown in Eq.(20)and thus K d variesinversely with [NO 3−]2according to Eq.(21)1þX 4i ¼1b i ½NO −3 i !Y ½NO −34ð20ÞK d ∝K ½Im ÀNO 3 ½NO −3−2ð21ÞThus,depending upon the nitrate ion concentration used in the study the slope of the plot of log K d versuslog [NO 3−]should vary from 2to −2according to Eqs.(19)and (21).A plot log K d against log [NO 3]is shown in Fig.3.When the initial concentration of nitric acid is 1.0M,and the total nitrate in the test solution is varied from 1.0M to 5.0M,log K d −log [NO 3]results in a slope of 0.91.The magnitude of slope decreases to 0.4when the initial concentration of nitric acid is increased to 3.0M and the total nitrate ion concentration is varied up to 5.0M using sodium nitrate.Further increase in total nitrate concentration to 6.0M,when initial concentra-tion of nitric acid is 5.0M,results in a negative slope of −0.68.The results suggest that an increase in K d values of palladium with the increase in concentration of nitric acid could be attributed to the increased formation ofanionic palladium nitrate complexes,and decrease in K d values at higher nitrate ion concentrations could be due to the shift in the equilibrium reaction (14)in the reverse direction.3.4.Effect of [Im –NO 3]At constant nitrate ion concentration,a plot of log K d against log [Im –NO 3]should result in a slope of unity,according to Eq.(17).Fig.4shows the plot of log K d against log [Im –NO 3]for the extraction of palla-dium at various initial concentrations of nitric acid.It is seen that K d value increases with increase in the extent of functionalization.At all nitric acid concentrations,log K d −log [Im –NO 3]plot results in a slope of ∼1.0,which is in accordance with Eq.(14),confirming the validity of the mechanism shown in Eq.(14).Similarly,slope analysis for the extraction of palladium (II)by solvent extraction (Mohan Raj et al.,2006;Giridhar et al.,2006b )using liquid anion exchangers have resulted in a slope of 1.5.It was proposed the extraction of both [Pd(H 2O)(NO 3)3]−and [Pd(NO 3)4]2−is responsible for the higher magnitude.However,in the present study,the PS –DVB resin matrix being rigid,seems to prefer the extraction of [Pd(H 2O)(NO 3)3]−resulting in a slope of 1.0only.3.5.Effect of [Pd(II)]The variation of palladium loading in Im –NO 3resin as a function of its concentration is shown in Fig.5.The amount of palladium loaded on to the resin increases with the concentration of palladium in the aqueous phase.The linear form of the Langmuir equationrelatingFig.3.Variation of log K d with log [NO 3]for the extraction of palladium (II)by Im –NO 3.V /m =200mL/g;T =298K;equilibration time=10h;[Pd(II)]=6.2×10−4M.Fig.4.Variation of log K d with log [Im –NO 3]for the extraction ofpalladium (II)by Im –NO 3.V /m =200mL/g;T =298K;equilibration time=10h;[Pd(II)]=6.2×10−4M.226K.A.Venkatesan et al./Hydrometallurgy 86(2007)221–229the amount of metal ion extracted (C s )by the resin and the metal concentration in solution (C f )is given by Eq.(22).C f C s ¼1K L b þC fbð22Þwhere C f is the equilibrium concentration of palladium (mg/L),C s is the amount of palladium extracted by Im –NO 3(mg/g),K L is the Langmuir adsorption con-stant (L/mg)is related to the affinity of the resin towards the metal ion,and b is the apparent extraction capacity of palladium on Im –NO 3resin under the studied condi-tions.From Eq.(22),the experimental capacity (b ,mg/g)and K L are obtained from the slope and intercepts of the straight line shown in Fig.6.The apparent experi-mental capacity,b ,was found to be 88mg/g for the extraction of palladium (II)from 3.0M nitric acid medium by Im –NO 3resin.3.6.Column experimentsThe performance of the resin under dynamic loading conditions can be evaluated by following a breakthrough curve (Helfferich,1962).Fig.7shows the breakthrough curve for the extraction of palladium (II)(6.2×10−4M)from 3.0M nitric acid medium by Im –NO 3.The feed solution was passed at a flow rate of 0.5mL/min.It is seen that 10%breakthrough is obtained after passing 25bed volumes.Various simple models have been developed to describe the dynamic behavior of extraction of metal ions in a fixed bed column (Thomas,1944;Aksu and Gonen,2004;Mathaialagan and Viraraghavan,2002;Sivaiah et al.,2004).The Thomas model (Thomas,1944)is given by Eq.(23)C C 0¼11þe T o V Þ=Q Þð23Þwhere,C and C 0are the concentration of palladium (in mg/L)in the effluent and in the feed (=65mg/L),respectively;K T is the Thomas rate constant (mL min −1mg −1);B (in mg/g)is the maximum loading capacity of palladium under the specified conditions;m (=1.0g)is the mass of the sorbent taken in the column;V (in mL)is the throughput volume and Q is the flow rate in mL/min.Breakthrough data is fitted using Eq.(23)by non-linear regression and the values of K T and B were found to be 1.72×10−1mL min −1mg −1and 8mg/g respectively.The extracted palladium was quantitatively eluted using 25mL of 0.05M thiourea in 0.1M nitricacid.Fig.5.Ion exchange isotherm of palladium (II)extraction from 3.0M nitric acid.V /m =200mL/g;T =298K;equilibration time=10h.ngmuir plot for the extraction of palladium from 3.0M nitric acid.V /m =200mL/g;T =298K;equilibration time=10h.Fig.7.Breakthrough curves for the extraction of palladium (II)by Im –NO 3.Resin =1g =2mL;T =298K;[HNO 3]=3.0M;flow rate =0.5mL/min;[Pd(II)]=6.2×10−4M.227K.A.Venkatesan et al./Hydrometallurgy 86(2007)221–2294.ConclusionsThe kinetics of anchoring of1-methylimidazole on chloromethylated polystyrene–divinylbenzene is rapid and leads to80%anchoring of methylimidazolium ion on the resin matrix within40min of refluxing.A maximum anion exchange capacity of∼4mmol/g was obtained after5h of the reaction.The distribution coefficient of palladium(II)in the resin increased with the aqueous phase concentration of nitric acid and reached a maximum at3–4M.Anion exchange of palladium nitrate species,[Pd(H2O)(NO3)3]−,present in aqueous phase with NO3−ion of Im–NO3resin is responsible for the extraction of palladium(II)from nitric acid medium.The extraction data can be fitted to a Langmuir adsorption model and an apparent exchange capacity of88mg/g for palladium extraction from3.0M nitric acid is obtained.Breakthrough curve is followed up to the C/C o of0.8and10%breakthrough is obtained after passing25bed volumes of the feed. 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