EP3802477A1 - Procédé de préparation de l'acétylacétonate d'un élément chimique hydraté ou anhydre - Google Patents
Procédé de préparation de l'acétylacétonate d'un élément chimique hydraté ou anhydreInfo
- Publication number
- EP3802477A1 EP3802477A1 EP19735369.1A EP19735369A EP3802477A1 EP 3802477 A1 EP3802477 A1 EP 3802477A1 EP 19735369 A EP19735369 A EP 19735369A EP 3802477 A1 EP3802477 A1 EP 3802477A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydroxide
- oxide
- acetylacetone
- reaction
- acetylacetonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052729 chemical element Inorganic materials 0.000 title claims abstract description 37
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 150
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 12
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 11
- 239000012736 aqueous medium Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- PKQIDSVLSKFZQC-UHFFFAOYSA-N 3-oxobutanal Chemical compound CC(=O)CC=O PKQIDSVLSKFZQC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 72
- 239000000706 filtrate Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000011777 magnesium Substances 0.000 claims description 35
- 238000001914 filtration Methods 0.000 claims description 23
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000008346 aqueous phase Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 11
- 239000000347 magnesium hydroxide Substances 0.000 claims description 11
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 11
- 238000010923 batch production Methods 0.000 claims description 8
- -1 cobalt acetylacetonate dihydrate Chemical class 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- PKSIZOUDEUREFF-UHFFFAOYSA-N cobalt;dihydrate Chemical compound O.O.[Co] PKSIZOUDEUREFF-UHFFFAOYSA-N 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- OJWXYTCJBBNRNX-UHFFFAOYSA-N 6,12-dimethylanthanthrene Chemical compound C1=C2C(C)=C(C=CC=C3C=CC4=C5C)C3=C4C2=C2C5=CC=CC2=C1 OJWXYTCJBBNRNX-UHFFFAOYSA-N 0.000 claims description 5
- 239000012429 reaction media Substances 0.000 claims description 5
- 238000010924 continuous production Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- LDRHDOBLZDBGOP-VGKOASNMSA-L magnesium;(z)-4-oxopent-2-en-2-olate;dihydrate Chemical compound O.O.[Mg+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O LDRHDOBLZDBGOP-VGKOASNMSA-L 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 150000004683 dihydrates Chemical group 0.000 description 4
- 125000002587 enol group Chemical group 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 3
- 241000277326 Oncorhynchus gorbuscha Species 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- QBXAXCNNACSYCJ-UHFFFAOYSA-N pentane-2,4-dione;hydrate Chemical compound O.CC(=O)CC(C)=O QBXAXCNNACSYCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/77—Preparation of chelates of aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/92—Ketonic chelates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
Definitions
- the invention relates to a process for the preparation of acetylacetonate of a hydrated or anhydrous chemical element from oxide or hydroxide of the chemical element, acetylacetone and water.
- the invention also relates to a batch continuous process for the synthesis of such an acetylacetonate of a hydrated or anhydrous chemical element.
- a known synthesis route of cobalt (II) acetylacetonate dihydrate (AA 2 Co, 2H 2 O) is to react acetylacetone in alkaline (Na, K) or pseudo-alkaline (ammonium) type enolate form with dichloride. of cobalt.
- the disadvantage of this reaction is that it releases undesirable compounds, for example sodium chloride.
- This document also describes the preparation of magnesium acetylacetonate dihydrate (AA 2 Mg, 2H 2 O) from magnesium chloride in an aqueous medium.
- the magnesium hydroxide is formed by reaction between magnesium dichloride and potassium hydroxide.
- the magnesium hydroxide reacts in mass (without solvent) with the acetylacetone in enol form in slight excess to lead to the magnesium acetylacetonate dihydrate (AA 2 Mg, 2H 2 0).
- CN 1746180 also discloses a process for the preparation of cobalt (II) acetylacetonate dihydrate (AA 2 Co, 2H 2 O).
- US6376719 and US6093844 disclose methods for obtaining anhydrous alkaline earth metal acetylacetonate mass and high temperature drying or under high vacuum. They do not make it possible to obtain a hydrated product.
- the subject of the invention is therefore a process for preparing the acetylacetonate of a hydrated or anhydrous Me chemical element, wherein the chemical element Me is chosen from alkaline earth metals, transition metals and lanthanides, comprising a reaction step in an aqueous medium of the oxide or hydroxide of Me introduced in solid form and acetylacetone, acetylacetone being in excess relative to the oxide or the Me hydroxide.
- hydrated acetylacetonate Me is meant a product which comprises one or more molecules of water generally designated by water of crystallization.
- anhydrous Me acetylacetonate is meant a product which does not comprise water molecules.
- oxide or hydroxide of Me we mean the chemical element
- oxide or hydroxide of Me introduced in solid form means that the oxide or hydroxide of Me is not introduced into solution.
- alkaline earth metals that can be used according to the invention, mention may be made of magnesium, calcium, strontium and barium.
- transition metals that may be used according to the invention, mention may be made of cobalt, nickel, copper and zinc.
- lanthanides that can be used according to the invention, mention may be made of lanthanum, cerium, praseodymium and neodymium.
- the chemical element Me is preferably chosen from cobalt, magnesium, nickel, calcium, neodymium and zinc.
- the chemical element Me is cobalt.
- the compound obtained according to the process according to the invention is then acetylacetonate cobalt dihydrate (AA 2 Co, 2H20).
- the precipitate of this compound has a pink salmon color.
- this compound is obtained by reaction between cobalt (II) hydroxide (Co (OH) 2 ) and acetylacetone in water.
- the chemical element Me is magnesium.
- the compound obtained according to the process according to the invention is then magnesium acetylacetonate dihydrate (AA 2 Mg, 2H 2 O).
- the precipitate of this compound has a white color.
- this compound is obtained by reaction between magnesium (II) hydroxide (Mg (OH) 2 ) or magnesium oxide MgO and acetylacetone in water.
- magnesium oxide When magnesium oxide is used as a starting material, it reacts with water to form magnesium (II) hydroxide (Mg (OH) 2 ) which in turn will react with acetylacetone in water for form the final product (AA 2 Mg, 2H 2 O).
- the acetylacetone is in excess with respect to the Me oxide or hydroxide.
- the acetylacetone / oxide or hydroxide molar ratio of Me is greater than 2 when the oxide or hydroxide of Me is divalent and greater than 3 when the oxide or hydroxide of Me is trivalent, more preferably greater than or equal to 4 when the oxide or hydroxide of Me is divalent and greater than or equal to 6 when the oxide or hydroxide of Me is trivalent, more preferably equal to 6 when the oxide or hydroxide of Me is divalent and equal to 9 when the oxide or hydroxide of Me is trivalent.
- AAH represents acetylacetone in enol form.
- the reaction time is generally between 2h and 6h, preferably of the order of 4h.
- a filtration step is generally carried out to recover a solid phase comprising Me hydrated acetylacetonate and a liquid filtrate comprising water, acetylacetone in excess and a Me acetylacetonate hydrate fraction. solubilized.
- the liquid filtrate must be homogeneous, that is to say, have only one phase.
- the weight of acetylacetone in the aqueous phase of the liquid filtrate must advantageously remain less than or equal to 15% of the weight of the aqueous phase. Beyond this, filtration is more difficult and recycling must take into account that the filtrate can be biphasic.
- the aqueous dilution of the initial reaction medium (Me oxide or hydroxide and acetylacetone in water) must be adapted accordingly.
- the Me acetylacetonate present in the solid phase is in a hydrated form. It is then usually dried.
- This drying can be carried out by applying a vacuum and / or reducing the vapor pressure by a flow of gas, preferably inert, and / or by increasing the temperature of the product to remove the free water (obtaining the dried hydrated product), and also the water of crystallization in the case of an anhydrous end product.
- the drying temperature is generally less than 75 ° C.
- the drying temperature is generally below 65 ° C.
- the product obtained, hydrated or anhydrous Me acetylacetonate, is in the form of a powder of fine non-agglomerated particles.
- This recovered product is very pure, with a purity close to 100%, and requires no washing because there is no secondary reaction product (such as sodium chloride).
- the liquid filtrate obtained at the end of the filtering stage is advantageously entirely recycled for the following synthesis as well as the vapors obtained at the end of the drying. This recycling operation is repeated at each new synthesis so that there is no loss of chemical element Me or acetylacetone.
- the condensates obtained during the drying step essentially contain water and a little acetylacetone. In an industrial implementation, they can advantageously be fully recycled in the following syntheses.
- the subject of the invention is also a batch continuous process for the synthesis of acetylacetonate of a hydrated or anhydrous Me chemical element, in which the chemical element Me is chosen from alkaline earth metals, transition metals and lanthanides, said process comprising n successive steps of reaction in an aqueous medium of the oxide or hydroxide of Me introduced in solid form and acetylacetone, the acetylacetone being in excess relative to the oxide or hydroxide of Me, a filtration being carried out at the end of each reaction i, i ranging from 1 to n, the liquid filtrate recovered at the end of the reaction i ', i' varying from 1 to n-1, and comprising water, acetylacetone in excess and a solubilized hydrated Me acetylacetonate fraction, being recycled by adding to the reaction medium of the reaction i '+ 1, n being greater than or equal to 2.
- batch continuous process is meant in the sense of the present invention a process comprising
- alkaline earth metals that can be used according to the invention, mention may be made of magnesium, calcium, strontium and barium.
- the chemical element Me is preferably chosen from cobalt, magnesium, nickel, calcium, neodymium and zinc.
- n ranges from 2 to 60, more preferably from 2 to 40, more preferably from 2 to 20.
- the acetylacetone / oxide or hydroxide molar ratio of Me is greater than 2 when the oxide or hydroxide of Me is divalent and greater than 3 when the oxide or hydroxide of Me is trivalent, preferably greater than or equal to 4 when the oxide or hydroxide of Me is divalent and greater than or equal to 6 when the oxide or hydroxide of Me is trivalent, more preferably equal to 6 when the oxide or hydroxide of Me is divalent and equal to 9 when the oxide or Me hydroxide is trivalent.
- Filtration is carried out after each reaction i. Filtration makes it possible to recover acetylacetonate from the chemical element
- the weight of acetylacetone in the aqueous phase of the liquid filtrate is less than or equal to 15% of the weight of the aqueous phase.
- the continuous batch process according to the invention thus makes it possible to recycle the filtrate of each synthesis reaction of the Me acetylacetonate hydrate in the following reaction.
- the yield is thus quasi-quantitative.
- the process does not require specific treatment of waste effluents.
- the acetylacetonate of the hydrated Me chemical element recovered after filtration after each reaction is preferably dried.
- the invention further relates to a process for the preparation of acetylacetonate of a hydrated or anhydrous Me chemical element, wherein the chemical element Me is selected from alkaline earth metals, transition metals and lanthanides, from of Me oxide or hydroxide and acetylacetone, wherein said Me acetylacetonate is obtained as well as a liquid filtrate containing acetylacetone in aqueous phase and a condensate, the liquid filtrate being capable of being used for a new acetylacetonate preparation of the Me element as a reagent.
- the chemical element Me is selected from alkaline earth metals, transition metals and lanthanides, from of Me oxide or hydroxide and acetylacetone, wherein said Me acetylacetonate is obtained as well as a liquid filtrate containing acetylacetone in aqueous phase and a condensate, the liquid filtrate being capable of being used for a new acety
- said process comprises a first step of reaction in an aqueous medium of the oxide or hydroxide of the element Me introduced in solid form and acetylacetone, the acetylacetone being in excess relative to the oxide or the Me hydroxide, and a second filtration step.
- the weight of acetylacetone in the aqueous phase of the liquid filtrate is advantageously less than or equal to 15% of the weight of the aqueous phase.
- the condensate may be used for a new acetylacetonate preparation of the Me element as a reagent.
- magnesium contained in magnesium acetylacetonate is released in the aqueous phase by dissolving with acetone and then hydrolysed with a hydrochloric acid solution.
- the manipulation consists in a determination of the magnesium ions (Mg2 +) of the sample by EDTA in the presence of a colored indicator: the Black Eriochrome T (denoted NET).
- the end of dosing detection is performed by a phototrode set at 660nm.
- the magnesium ions preferentially complex with EDTA. At the end of the assay, all magnesium ions will have complexed with EDTA.
- the colored indicator (NET) will resume its free form and initial color: bluish. This color change is followed by the phototrode mentioned above.
- the hydrotimetric titer is the amount of EDTA (noted as H2Y2-) used to reach the turn.
- cobalt contained in cobalt acetylacetonate is released in aqueous phase by dissolution in acetone and then hydrolysed with a hydrochloric acid solution.
- the manipulation consists of a determination of the cobalt ions of the sample by EDTA in the presence of a colored indicator: orange xylenol. End-of-dosing detection is performed by visual observation of a color change.
- Cobalt ions preferentially complex with EDTA. At the end of the assay, all cobalt ions will have complexed with EDTA.
- the colored indicator (orange xylenol) will resume its free form and its initial color: orange. This color change is followed visually.
- the hydrotimetric titer is the amount of EDTA (noted as H2Y2-) used to reach the turn.
- Mg level by spectrophotometry in magnesium acetylacetonate Magnesium acetylacetonate is hydrolysed in an acidified aqueous solution (for example with hydrochloric acid) while hot. Once the complete dissolution of the magnesium acetylacetonate has been achieved, the solution thus obtained is analyzed by ICP (Inductively Coupled Plasma) coupled to a spectrophotometric atomic emission detector (AES). When introduced into the ICP-AES elements present in the solution will be excited in contact with the plasma. When they return to their ground state, they will emit radiation whose wavelength is representative of their chemical nature. Thus, by detecting the intensity of the radiation at the wavelength corresponding to magnesium, it will be possible to determine the content within the solution.
- ICP Inductively Coupled Plasma
- AES spectrophotometric atomic emission detector
- Cobalt acetylacetonate is hydrolysed in an acidified aqueous solution (for example with nitric acid).
- an acidified aqueous solution for example with nitric acid.
- ICP Inductively Coupled Plasma
- AES spectrophotometric atomic emission detector
- the initial aqueous dilution is advantageously calculated so as to keep a homogeneous aqueous phase for the filtrate. This limit is reached when the weight of acetylacetone in water approaches 15%. When this limit is exceeded, a supernatant organic phase will appear in the filtrate. This situation can make filtration more difficult.
- the experimental conditions are as follows:
- the hydroxide of Mg is completely added to the filtrate of reaction 1 (first without stirring) and then acetylacetone and the balance of water (correction of the loss due to drying since in this example it is not There is no recycling of the condensate) are added with stirring in this suspension.
- the reaction time is 4 hours.
- Acetylacetone and the balance of water are added to the filtrate of reaction 2 with stirring (the inverse, namely the filtrate in acetylacetone and additional water is also possible).
- the hydroxide of Mg is added in small portions in the water-acetylacetone reaction medium (slightly biphasic but well stirred at ⁇ 500tr / min).
- the addition (spatulate) lasts between l 0-15 min.
- the total reaction time (4h) includes this addition time.
- the magnesium acetylacetonate obtained is dried to obtain either an anhydrous form or a dihydrate form with the latter less severe drying conditions.
- the drying conditions in an oven are a temperature of 50 ° C. under vacuum of approximately 60 mbar. regulated with a slight nitrogen sweep, until a constant mass is obtained.
- the drying conditions in an oven are a temperature of 50 ° C under vacuum of about 500 mbar regulated with a slight nitrogen sweep, until a constant mass is obtained.
- the yield of magnesium acetylacetonate (anhydrous or dihydrate) calculated from the amount of the introduced magnesium hydroxide is given for each reaction in Table 2. For example, the yield for reaction 7 is 96% (79%). 5 g of product obtained) if it is considered that the product is in the dihydrate form (258.55 g / mol). The theoretical rate of magnesium is 9.40%. This yield illustrates the loss of magnesium acetylacetonate by solubilization in the filtrates and the interest of recovering these filtrates. Table 2
- the aqueous filtrate containing the excess of acetylacetone and solubilized cobalt acetylacetonate is entirely recycled in a following synthesis.
- the operation is repeated 3 times.
- the initial aqueous dilution is advantageously calculated so as to keep a homogeneous aqueous phase for the filtrate. This limit is reached when the weight of acetylacetone in water approaches 15%. When this limit is exceeded a supernatant organic phase will appear in the filtrate. This situation can make filtration more difficult.
- the experimental conditions are as follows: Reaction 1:
- the Co (II) hydroxide is totally added to the filtrate of reaction 1 (suspension with stirring) and then acetylacetone and the addition of water (correction of the loss due to drying in that in this case example there is no recycling of condensate) are added with stirring in this suspension.
- the reaction time is 4 hours at room temperature with stirring ( ⁇ 500 rpm).
- the cobalt acetylacetonate obtained is dried to obtain an anhydrous form.
- the drying conditions in an oven are a temperature of 50 ° C under vacuum of about 250 mbar regulated with a slight sweep of air or nitrogen) to a constant mass.
- the color of the product obtained shows that the product obtained is the acetylacetonate cobalt dihydrate.
- the yield of cobalt (II) acetylacetonate calculated from the amount of cobalt (II) hydroxide introduced is given for each reaction in Table 4. For example, the yield for reaction 3 is 97% (91%). g of product obtained) if it is considered that the product is in the dihydrate form (293.18 g / mol). The theoretical cobalt level is 20, 10%.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Catalysts (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1854881A FR3081868B1 (fr) | 2018-06-05 | 2018-06-05 | Procede de preparation de l'acetylacetonate d'un element chimique hydrate ou anhydre |
PCT/FR2019/051345 WO2019234356A1 (fr) | 2018-06-05 | 2019-06-05 | Procédé de préparation de l'acétylacétonate d'un élément chimique hydraté ou anhydre |
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EP3802477A1 true EP3802477A1 (fr) | 2021-04-14 |
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EP19735369.1A Pending EP3802477A1 (fr) | 2018-06-05 | 2019-06-05 | Procédé de préparation de l'acétylacétonate d'un élément chimique hydraté ou anhydre |
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US (1) | US20210238118A1 (ko) |
EP (1) | EP3802477A1 (ko) |
KR (1) | KR20210018258A (ko) |
FR (1) | FR3081868B1 (ko) |
WO (1) | WO2019234356A1 (ko) |
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US3474464A (en) * | 1967-08-03 | 1969-10-21 | Grace W R & Co | Process for preparing acetylacetonates |
DE2420775C3 (de) * | 1974-04-29 | 1980-01-31 | Wacker-Chemie Gmbh, 8000 Muenchen | Verfahren zur Herstellung von Mangan (Ill)acetylacetonat |
WO1989007666A1 (en) * | 1988-02-19 | 1989-08-24 | Northwestern University | Method of forming superconducting materials |
DE19610320C2 (de) | 1996-03-15 | 1998-01-22 | Henkel Kgaa | Verfahren zur Herstellung von Erdalkalimetallsalzen aliphatischer beta-Ketoverbindungen |
JP2000026362A (ja) | 1998-07-10 | 2000-01-25 | Daicel Chem Ind Ltd | β−ジケト化合物のアルカリ土類金属塩の製造方法 |
WO2004056737A1 (en) * | 2002-12-23 | 2004-07-08 | Council Of Scientific And Industrial Research | Process for the preparation of metal acetylacetonates |
CN1313473C (zh) * | 2005-05-19 | 2007-05-02 | 北京化工大学 | 一种乙酰丙酮钴的制备方法 |
US7442820B1 (en) * | 2008-01-25 | 2008-10-28 | W.C. Heraeus Gmbh | Process for the preparation of platinum acetylacetonato complexes |
-
2018
- 2018-06-05 FR FR1854881A patent/FR3081868B1/fr active Active
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2019
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- 2019-06-05 WO PCT/FR2019/051345 patent/WO2019234356A1/fr unknown
- 2019-06-05 KR KR1020207034695A patent/KR20210018258A/ko unknown
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US20210238118A1 (en) | 2021-08-05 |
FR3081868B1 (fr) | 2020-11-06 |
KR20210018258A (ko) | 2021-02-17 |
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