WO1998051646A1 - Process for the removal of heavy metals - Google Patents
Process for the removal of heavy metals Download PDFInfo
- Publication number
- WO1998051646A1 WO1998051646A1 PCT/EP1998/002628 EP9802628W WO9851646A1 WO 1998051646 A1 WO1998051646 A1 WO 1998051646A1 EP 9802628 W EP9802628 W EP 9802628W WO 9851646 A1 WO9851646 A1 WO 9851646A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- compound
- aqueous solution
- removal
- palladium
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 27
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 25
- 238000011282 treatment Methods 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 18
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 claims description 15
- 229960004308 acetylcysteine Drugs 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001944 cysteine derivatives Chemical class 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 abstract description 4
- 235000018417 cysteine Nutrition 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000000144 pharmacologic effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- LJWSDBHOEIBWJY-UHFFFAOYSA-N 2-benzamido-3-sulfanylpropanoic acid Chemical compound OC(=O)C(CS)NC(=O)C1=CC=CC=C1 LJWSDBHOEIBWJY-UHFFFAOYSA-N 0.000 description 1
- 238000008947 Amm Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hexane Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HQDXNTRZJRNPLD-UHFFFAOYSA-N n-[2-(3,4-dimethoxyphenyl)ethyl]-4-[5-methoxy-2-(2-phenylethynyl)phenyl]-n-methylbutan-2-amine Chemical compound C=1C=C(OC)C(OC)=CC=1CCN(C)C(C)CCC1=CC(OC)=CC=C1C#CC1=CC=CC=C1 HQDXNTRZJRNPLD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002993 phenylalanine derivatives Chemical class 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
Definitions
- the present invention relates to a process for the removal of heavy metals from organic compounds by treatment with cysteme or N-acylcysteine and, more particularly, it relates to a process for the removal of heavy metals from solutions of organic compounds in solvents immiscible with water
- the heavy metals are widely used in industrial synthetic processes for the preparation of compounds useful in different fields Because of the easy formation of complexes, a very common drawback bound to the use of these heavy metals is that they often remain present in relevant amounts in the organic compounds
- object of the present invention is a process for the removal of heavy metals from organic compounds characterised in that a solution of the organic compound in a solvent immiscible with water is treated with a cysteine derivative of formula
- R is a hydrogen atom, a linear or branched C ⁇ -C ft acvl group or a benzoyl group
- the compounds of formula I are known or they can be easy prepared by known methods. specific examples including cysteine, N-acetylcysteine, N-benzoylcysteine, N-p ⁇ valoylc ⁇ steme and N-propionylcysteme
- cysteine or N-acetylcysteine are used in the process of the present invention
- the amount of cysteine derivative of formula I to be used depends on the amount of heavy metal to be removed but it is at least equimolar with respect to the heavy metal
- a molar ratio compound I heavy metal from 5 1 to 15 1 is used
- the organic compound containing the impurity of the heavy metal must be dissolved in a solvent immiscible with water or in a mixture of solvents of which at least one is immiscible with water
- the selection of the suitable organic solvent or of the mixture of solvents depends exclusively on the solubility characteristics of the compound to be purified Examples of these solvents are toluene, xylene, methylene chloride, chlorobenzene. 1.2- dichlorobenzene and aliphatic hydrocarbons such as hexane, optionally in admixture with aprotic dipolar solvents such as dimethylsulphoxide. tetrahydrofuran and acetonit ⁇ le
- the compound of formula I can be used as such, that is as a powder, or more preferably dissolved in water, that is as an aqueous solution
- the concentration of the aqueous solution of the compound of formula I is generally between 5% and 70% w/w From a practical viewpoint, the use of concentrated solutions, preferably with concentrations between 20% and 60% w/w, is preferred
- the aqueous solution of the compound of formula I can be prepared separately so carrying out the treatment for the removal of the heavy metals by washing the solution containing the organic compound with the aqueous solution of compound I Alternatively, the suitable amount of compound of formula I and the necessary amount of water can be added separately to the solution of the organic compound to be purified
- the removal treatment can be simply carried out by adding the suitable amount of compound of formula I directly to the solution of the organic compound
- the heavy metal remains in the aqueous phase, likely in the form of a complex with the compound of formula I, while the organic compound remains in solution in the organic phase
- the treatment time can be variable but generally an increase of the amount of removed heav> metal is observed when the treatment time is increased In the same manner, the treatment time and the molar ratio of compound I remaining the same. an increase of the amount of removed heavy metal is observed when the treatment temperature is increased
- the process for the removal of the heavy metals according to the present invention is carried out at a temperature between the room value and the reflux temperature of the mixture, preferably between 20°C and 60°C Depending on their initial content, the desired low values of the heavy metals can be reached after one treatment or after more treatments according to the process object of the present invention Furthermore, we have found that the efficacy of the treatment for the removal of the heavy metals according to the process object of the present invention can be further increased by carrying out a final washing with an aqueous basic solution
- Suitable basic solutions are aqueous solutions of ammonia, aqueous solutions of ammes. such as t ⁇ ethylamine, and aqueous solutions of inorganic bases such as sodium or potassium carbonates, bicarbonates and hydroxides
- an aqueous 30% ammonia solution which is directly added at the end of the treatment with the aqueous solution of compound I, that is before the separation of the phases,
- the process object of the present invention is useful for the removal of several heavy metals which are commonly used as reagents such as tin, palladium and other metals which can be retained as impurities in the form of complexes with organic compounds
- palladium is also the heavy metal which more frequently remains as impurity of difficult removal in the organic compounds
- the method object of the present invention proved to be particularly efficient in the removal of high amounts of palladium present in heteroarylphenylalamnes prepared b ⁇ coupling a phenylalanine derivative with a heteroarvl-zinc hahde in the presence of a palladium(0)based catalyst (International patent applications no PCT/EP97/07024 and no PCT/EP98/00126 in the name of the present Applicant, filed on December 12, 1997 and on January 12, 1998 respectively)
- the process object of the present invention proved to be equally efficient in the removal of palladium, present as an impurity, from intermediates for the synthesis of diflumsal and from mtenriediates for the synthesis of 5,8-d ⁇ hydro-2.4-d ⁇ methyl-8-[(2 , -(lH-tetrazol-5- ⁇ l)[l,r- b ⁇ phenyl]-4-yl]methyl]pyr ⁇ do[2,3-d]pyr ⁇ m ⁇ d ⁇ n-7(6H)-one prepared by coupling reaction in the presence of palladium(0)based catalysts according to the processes described in the European patent application 0 494 419 (Zambon Group S p A ) and in the patent application WO 96/40684 (American Home Products Corporation), respectively
- a solution of the organic compound containing palladium is heated to a temperature between
- Example 1 Bromoethane (1 33 g, 0 0122 moles) was added to a mixture of tetrahydrofuran (18 2 ml), toluene (18 2 ml) and magnesium (1 76 g, 0 0724 moles) The temperature arose up to 60°C and the mixture was cooled to 35°C and added with 2-bromoth ⁇ azole (10 g, 0 061 moles) in 1 5 hours
- Example 2 A mixture of tetrahydrofuran (1 1 ml), toluene (5 ml) and zmc (1 56 g, 0 0238 moles) was heated under reflux and added with 2-bromoth ⁇ azole (3 6 g, 0 022 moles) in about 1 5 hours The mixture was kept under stirring under reflux for 1 hour and cooled at 50°C N-formyl-4- lodo-L-phenylalanine methyl ester (5 8 g, 0 0174 moles) and, subsequently, palladium acetate (0 035 g, 0 15 mmoles) and t ⁇ phenylphosphine (0 092 g, 0 35 mmoles) were added The mixture was kept under stirring for 1 hour, the suspension was cooled at 30°C and poured into water ( 10 ml) Acetic acid (0 5 ml) was added and the phases were separated The organic phase was brought to residue under vacuum and the residue (containing 3290 ppm palladium) was taken with
- the Pd content was brought from the initial content of 777 ppm to a value of 31 ppm
- the internal temperature was brought to 60°C and, under stirring N-acetylcysteine (15 7 g, 0 0962 moles) and water (8 0 g) were added
- Example 6 In an anhydrous 250 cc reactor, magnesium turnings (9 9 g, 0 406 moles), tetrahydrofuran (60 g) and toluene (60 g) were charged under nitrogen flux
- reaction mixture was kept under stirring at 95 °C for further 5 hours, then cooled to 85°C, and water (80 g) was added by contemporaneously distilling off tetrahydrofuran
- reaction mixture was acidified with 37% hydrochloric acid (4 1 g) before carrying out the separation of the phases
- the organic phase (152 g) was divided out. after dilution with toluene (100 0 g). into two portions of 125 g each, a portion was treated with N-acetylcysteme (1 12 g) and water (0 60 g) at 60°C for 8 hours while the other portion is treated with water (0 60 g) at 60°C for 8 hours m order to obtain comparative data At the end of the treatment, the two different portions were cooled at 40°C and washed with 15% ammonia (8 g)
- the organic solution treated with N-acetylcysteine had a palladium content equal to 50 ppm (3 5% of the initial content) while the comparative solution had a palladium content equal to 965 ppm (68 9% of the initial content)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Removal Of Specific Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Priority Applications (18)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/423,315 US6239301B1 (en) | 1997-05-13 | 1998-05-04 | Process for the removal of heavy metals |
| EA199900892A EA002285B1 (ru) | 1997-05-13 | 1998-05-04 | Способ удаления тяжелых металлов из органических соединений |
| EP98922798A EP0981507B1 (en) | 1997-05-13 | 1998-05-04 | Process for the removal of heavy metals |
| CA002288647A CA2288647C (en) | 1997-05-13 | 1998-05-04 | Process for the removal of heavy metals |
| IL13256198A IL132561A (en) | 1997-05-13 | 1998-05-04 | Process for the purification from heavy metal ions of solutions of organic compounds in water immiscible solvents |
| JP54875398A JP2001524977A (ja) | 1997-05-13 | 1998-05-04 | 重金属除去方法 |
| RO99-01211A RO119714B1 (ro) | 1997-05-13 | 1998-05-04 | Procedeu pentru îndepărtarea metalelor grele din soluţii de compuşi organici |
| AT98922798T ATE273944T1 (de) | 1997-05-13 | 1998-05-04 | Verfahren zur entfernung von schwermetallen |
| DE69825745T DE69825745T2 (de) | 1997-05-13 | 1998-05-04 | Verfahren zur entfernung von schwermetallen |
| SK1539-99A SK282370B6 (sk) | 1997-05-13 | 1998-05-04 | Spôsob odstraňovania ťažkých kovov z organických zlúčenín |
| HU0002119A HU222599B1 (hu) | 1997-05-13 | 1998-05-04 | Eljárás nehézfémek eltávolítására |
| NZ500565A NZ500565A (en) | 1997-05-13 | 1998-05-04 | Process for the removal of heavy metals from organic material where the organic compound in a solvent is treated with a cysteine derivative |
| SI9830707T SI0981507T1 (en) | 1997-05-13 | 1998-05-04 | Process for the removal of heavy metals |
| AU75302/98A AU739778B2 (en) | 1997-05-13 | 1998-05-04 | Process for the removal of heavy metals |
| DK98922798T DK0981507T3 (da) | 1998-05-04 | 1998-05-04 | Fremgangsmåde for fjernelse af tungmetaller |
| PL98336475A PL188425B1 (pl) | 1997-05-13 | 1998-05-04 | Sposób usuwania metali ciężkich, zwłaszcza palladu, ze związków organicznych |
| BR9808795-9A BR9808795A (pt) | 1997-05-13 | 1998-05-04 | Processo para remoção de metais pesados de compostos orgânicos |
| NO19995528A NO312509B1 (no) | 1997-05-13 | 1999-11-12 | Fremgangsmåte for fjerning av tungmetaller |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT97MI001108A IT1291356B1 (it) | 1997-05-13 | 1997-05-13 | Processo per la rimozione di metalli pesanti |
| ITMI97A001108 | 1997-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998051646A1 true WO1998051646A1 (en) | 1998-11-19 |
Family
ID=11377119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1998/002628 WO1998051646A1 (en) | 1997-05-13 | 1998-05-04 | Process for the removal of heavy metals |
Country Status (25)
| Country | Link |
|---|---|
| US (1) | US6239301B1 (en, 2012) |
| EP (1) | EP0981507B1 (en, 2012) |
| JP (1) | JP2001524977A (en, 2012) |
| CN (1) | CN1092624C (en, 2012) |
| AT (1) | ATE273944T1 (en, 2012) |
| AU (1) | AU739778B2 (en, 2012) |
| BG (1) | BG64772B1 (en, 2012) |
| BR (1) | BR9808795A (en, 2012) |
| CA (1) | CA2288647C (en, 2012) |
| CZ (1) | CZ294236B6 (en, 2012) |
| DE (1) | DE69825745T2 (en, 2012) |
| EA (1) | EA002285B1 (en, 2012) |
| ES (1) | ES2227832T3 (en, 2012) |
| HU (1) | HU222599B1 (en, 2012) |
| IL (1) | IL132561A (en, 2012) |
| IN (1) | IN183465B (en, 2012) |
| IT (1) | IT1291356B1 (en, 2012) |
| NO (1) | NO312509B1 (en, 2012) |
| NZ (1) | NZ500565A (en, 2012) |
| PL (1) | PL188425B1 (en, 2012) |
| PT (1) | PT981507E (en, 2012) |
| RO (1) | RO119714B1 (en, 2012) |
| SK (1) | SK282370B6 (en, 2012) |
| WO (1) | WO1998051646A1 (en, 2012) |
| ZA (1) | ZA984039B (en, 2012) |
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| EP3528958A4 (en) * | 2016-10-20 | 2020-07-15 | NewSouth Innovations Pty Limited | PROCESS FOR REMOVING HEAVY METALS FROM AN AQUEOUS SOLUTION |
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| US6746966B1 (en) * | 2003-01-28 | 2004-06-08 | Taiwan Semiconductor Manufacturing Company | Method to solve alignment mark blinded issues and a technology for application of semiconductor etching at a tiny area |
| US20040157316A1 (en) * | 2003-02-07 | 2004-08-12 | Farone William A. | Sulfhydral containing compounds and methods of using same |
| WO2006048746A2 (en) * | 2004-11-02 | 2006-05-11 | Pfizer Inc. | Methods for the removal of heavy metals |
| EA202190643A1 (ru) * | 2018-09-11 | 2021-07-09 | Астразенека Аб | УЛУЧШЕННЫЙ СПОСОБ ПРОИЗВОДСТВА 3-[(1S)-1-ИМИДАЗО[1,2-a]ПИРИДИН-6-ИЛЭТИЛ]-5-(1-МЕТИЛПИРАЗОЛ-4-ИЛ)ТРИАЗОЛО[4,5-b]ПИРАЗИНА И ЕГО ПОЛИМОРФНЫХ ФОРМ |
| CN113960023B (zh) * | 2021-09-27 | 2023-11-14 | 西南大学 | 一种利用凝胶实现水样中重金属离子浓度快速检测的方法 |
| CN114524508A (zh) * | 2022-03-15 | 2022-05-24 | 江西理工大学 | 一种促进生物滤池中微生物挂膜的强化剂及方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH029890A (ja) * | 1988-03-31 | 1990-01-12 | Yoshitomi Pharmaceut Ind Ltd | 有機錫化合物の除去法 |
| EP0494419A2 (en) * | 1991-01-08 | 1992-07-15 | ZAMBON GROUP S.p.A. | Process for the preparation of 5-(2,4-difluorophenyl)-salicylic acid |
| WO1996040684A1 (en) * | 1995-06-07 | 1996-12-19 | American Home Products Corporation | Process for preparation of biphenyl derivatives |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2953554A (en) * | 1956-08-07 | 1960-09-20 | Goodrich Gulf Chem Inc | Method of removing heavy metal catalyst from olefinic polymers by treatment with an aqueous solution of a complexing agent |
| US5427247A (en) | 1993-05-25 | 1995-06-27 | Lockheed Idaho Technologies Company | Method for mobilization of hazardous metal ions in soils |
| US5760220A (en) | 1995-06-07 | 1998-06-02 | American Home Products Corporation | Process for preparation of biphenyl derivatives |
-
1997
- 1997-05-13 IT IT97MI001108A patent/IT1291356B1/it active IP Right Grant
-
1998
- 1998-05-04 EA EA199900892A patent/EA002285B1/ru not_active IP Right Cessation
- 1998-05-04 AU AU75302/98A patent/AU739778B2/en not_active Ceased
- 1998-05-04 BR BR9808795-9A patent/BR9808795A/pt not_active Application Discontinuation
- 1998-05-04 WO PCT/EP1998/002628 patent/WO1998051646A1/en active IP Right Grant
- 1998-05-04 ES ES98922798T patent/ES2227832T3/es not_active Expired - Lifetime
- 1998-05-04 PL PL98336475A patent/PL188425B1/pl not_active IP Right Cessation
- 1998-05-04 US US09/423,315 patent/US6239301B1/en not_active Expired - Lifetime
- 1998-05-04 EP EP98922798A patent/EP0981507B1/en not_active Revoked
- 1998-05-04 AT AT98922798T patent/ATE273944T1/de not_active IP Right Cessation
- 1998-05-04 PT PT98922798T patent/PT981507E/pt unknown
- 1998-05-04 NZ NZ500565A patent/NZ500565A/en not_active IP Right Cessation
- 1998-05-04 JP JP54875398A patent/JP2001524977A/ja active Pending
- 1998-05-04 IL IL13256198A patent/IL132561A/xx not_active IP Right Cessation
- 1998-05-04 CA CA002288647A patent/CA2288647C/en not_active Expired - Fee Related
- 1998-05-04 HU HU0002119A patent/HU222599B1/hu not_active IP Right Cessation
- 1998-05-04 SK SK1539-99A patent/SK282370B6/sk not_active IP Right Cessation
- 1998-05-04 CN CN98805030A patent/CN1092624C/zh not_active Expired - Fee Related
- 1998-05-04 DE DE69825745T patent/DE69825745T2/de not_active Revoked
- 1998-05-04 CZ CZ19994013A patent/CZ294236B6/cs not_active IP Right Cessation
- 1998-05-04 RO RO99-01211A patent/RO119714B1/ro unknown
- 1998-05-13 ZA ZA984039A patent/ZA984039B/xx unknown
- 1998-05-13 IN IN858CA1998 patent/IN183465B/en unknown
-
1999
- 1999-11-04 BG BG103858A patent/BG64772B1/bg unknown
- 1999-11-12 NO NO19995528A patent/NO312509B1/no not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH029890A (ja) * | 1988-03-31 | 1990-01-12 | Yoshitomi Pharmaceut Ind Ltd | 有機錫化合物の除去法 |
| EP0494419A2 (en) * | 1991-01-08 | 1992-07-15 | ZAMBON GROUP S.p.A. | Process for the preparation of 5-(2,4-difluorophenyl)-salicylic acid |
| WO1996040684A1 (en) * | 1995-06-07 | 1996-12-19 | American Home Products Corporation | Process for preparation of biphenyl derivatives |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 14, no. 137 (C - 0702) 15 March 1990 (1990-03-15) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3528958A4 (en) * | 2016-10-20 | 2020-07-15 | NewSouth Innovations Pty Limited | PROCESS FOR REMOVING HEAVY METALS FROM AN AQUEOUS SOLUTION |
| US11472723B2 (en) | 2016-10-20 | 2022-10-18 | Newsouth Innovations Pty Limited | Method for removing heavy metals from an aqueous solution |
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