EP3131852A1 - Procédé de préparation de particules synthétiques phyllominérales en continu - Google Patents
Procédé de préparation de particules synthétiques phyllominérales en continuInfo
- Publication number
- EP3131852A1 EP3131852A1 EP15725732.0A EP15725732A EP3131852A1 EP 3131852 A1 EP3131852 A1 EP 3131852A1 EP 15725732 A EP15725732 A EP 15725732A EP 3131852 A1 EP3131852 A1 EP 3131852A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solvothermal treatment
- particles
- conduit
- continuously
- reaction medium
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims description 74
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000012429 reaction media Substances 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 239000000725 suspension Substances 0.000 claims abstract description 36
- 229910052729 chemical element Inorganic materials 0.000 claims abstract description 29
- 239000000470 constituent Substances 0.000 claims abstract description 17
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 97
- 238000006243 chemical reaction Methods 0.000 claims description 81
- 239000002243 precursor Substances 0.000 claims description 53
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 50
- 239000000499 gel Substances 0.000 claims description 40
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 39
- 239000011707 mineral Substances 0.000 claims description 39
- 238000010335 hydrothermal treatment Methods 0.000 claims description 35
- 239000000017 hydrogel Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000011144 upstream manufacturing Methods 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000004760 silicates Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 8
- 239000006104 solid solution Substances 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 101001012040 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Immunomodulating metalloprotease Proteins 0.000 claims description 2
- 239000000454 talc Substances 0.000 description 51
- 229910052623 talc Inorganic materials 0.000 description 51
- 235000010755 mineral Nutrition 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- -1 carboxylate salt Chemical class 0.000 description 29
- 239000002609 medium Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000000975 co-precipitation Methods 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000004115 Sodium Silicate Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 235000019795 sodium metasilicate Nutrition 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 4
- 229940069446 magnesium acetate Drugs 0.000 description 4
- 239000011654 magnesium acetate Substances 0.000 description 4
- 235000011285 magnesium acetate Nutrition 0.000 description 4
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 4
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000010414 supernatant solution Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- MZZINWWGSYUHGU-UHFFFAOYSA-J ToTo-1 Chemical compound [I-].[I-].[I-].[I-].C12=CC=CC=C2C(C=C2N(C3=CC=CC=C3S2)C)=CC=[N+]1CCC[N+](C)(C)CCC[N+](C)(C)CCC[N+](C1=CC=CC=C11)=CC=C1C=C1N(C)C2=CC=CC=C2S1 MZZINWWGSYUHGU-UHFFFAOYSA-J 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical class [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/22—Magnesium silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/001—Controlling catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/42—Micas ; Interstratified clay-mica products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
Definitions
- the invention relates to a process for the preparation of phyllomineral synthetic particles such as phyllosilicates.
- the phyllosilicate mineral particles such as talc
- talc are for example used in the form of fine particles in many industrial sectors, such as: thermoplastics, elastomers, paper, paint, varnishes, textiles, metallurgy, pharmacy, cosmetics, phytosanitary products or fertilizers in which phyllosilicates such as talc are used, by incorporation into a composition, as an inert filler (for their chemical stability or for the dilution of active compounds of higher cost ) or functional loads (for example to enhance the mechanical properties of some materials).
- the term "phyllomineral particle” means any mineral particle having a crystalline structure comprising at least one tetrahedral layer and at least one octahedral layer. It can for example be phyllosilicates.
- non-swelling any phyllo silicate or mineral particle whose diffraction line (001) is not affected by a treatment by contacting with ethylene glycol or glycol, that is, whose interatomic distance corresponding to the (X-ray) diffraction line (001) does not increase after being in contact with ethylene glycol or glycol .
- Phyllosilicates 2 1, with the exception of smectites, are non-swelling, it is for example talc or other phyllosilicates belonging to the group of micas such as muscovite.
- Natural talc which is a hydroxylated magnesium silicate of the formula Si 4 Mg 3 O 10 (OH) 2 , belongs to the family of phyllosilicates.
- Phyllosilicates are constituted by a regular stack of elementary sheets of crystalline structure, the number of which varies from a few units to several thousand units.
- the group comprising in particular, talc, mica and montmorillonite is characterized in that each elemental sheet is constituted by the association of two layers of tetrahedra located on either side of a layer of octahedra. This group corresponds to phyllosilicates 2: 1, including smectites.
- phyllosilicates 2: 1 are also referred to as TOT (tetrahedron-octahedron-tetrahedron). Smectites are characterized in particular by the presence, between the elementary leaves, of interfoliar spaces which contain water and cations and which imply the property of swelling of the mineral.
- the octahedral layer of the phyllosilicates 2: 1 is formed of two planes of ions O 2 and OH " (in the molar proportion O 2 7 OH of 2/1), on either side of this median layer two-dimensional networks of tetrahedra, one of whose vertices is occupied by an oxygen of the octahedral layer, while the other three are occupied by substantially coplanar oxygens.
- phyllosilicates and in particular talc, are sought which have a high purity, fine particles (micrometric or even sub-micron in at least one direction), and good structural and crystalline properties.
- WO2013 / 004979 discloses a process for preparing a composition comprising synthetic mineral particles such as talc by a co-precipitation reaction of a precursor hydrogel in the presence of a carboxylate salt followed by a hydrothermal treatment of said precursor hydrogel to a temperature of 300 ° C and an autogenous pressure of the order of 8MPa.
- a method according to WO2013 / 004979 makes it possible to obtain synthetic mineral particles having satisfactory structural properties, especially close to those of natural talc. This process also makes it possible to reduce the preparation time of the synthetic mineral particles (from 3 to 10 days) and constitutes the fastest known process for obtaining phyllosilicate particles.
- a duration of several days and / or an anhydrous heat treatment (annealing) at 550 ° C. for 5 hours is necessary to increase the crystallinity of the synthesized particles so as to approach the structural characteristics of a natural talc.
- the invention aims to provide a method for preparing phyllomineral synthetic particles in larger amounts and / or in shorter times than other methods of the state of the art.
- the invention also aims at providing a process for the preparation of phyllomineral synthetic particles whose duration is considerably reduced compared with the preparation time required in a process for the preparation of such particles described in the state of the art.
- the invention therefore aims to provide such a method whose implementation is simple and fast, and is compatible with the constraints of an industrial scale operation.
- the aim of the invention is to propose a process for the preparation of phyllomineral synthetic particles of high purity and having a thin particle size and a low dispersion, as well as a crystalline structure very close to that of natural phyllominerals, in particular natural phyllosilicates, and particular of natural talc.
- the invention also aims at providing a preparation method for precisely adjusting the characteristics of phyllomineral synthetic particles, in particular synthetic phyllosilicate particles obtained.
- the invention also aims at providing a process for preparing compositions comprising phyllomineral synthetic particles having structural properties very close to those of natural phyllosilicates and in particular talc.
- the invention also aims in particular at providing a method for preparing compositions comprising synthetic phyllosilicate mineral particles that can be used in place of natural talc compositions, in various of their applications.
- the invention therefore also aims at providing compositions obtained by a process according to the invention.
- the invention relates to a process for preparing phyllomineral synthetic particles, formed of chemical elements, said constituent chemical elements, in predetermined proportions, called stoichiometric proportions, said constituent chemical elements comprising at least one chemical element selected from the group formed of silicon and germanium, and at least one chemical element selected from the group consisting of divalent metals and trivalent metals, by a treatment, called a solvothermal treatment, of a reaction medium comprising a liquid medium and containing said stoichiometric proportions of said elements constitutive chemicals of said phyllomineral synthetic particles, said phyllomineral synthetic particles belonging to the group of non-swelling phyllosilicates, and in particular belonging to the group of non-swelling phyllosilicates 2: 1, wherein:
- said solvothermal treatment is carried out continuously at a pressure greater than IMPa and at a temperature of between 100 ° C. and 600 ° C.
- the reaction medium is circulated continuously in a zone, called the solvothermal treatment zone, of a continuous reactor with a residence time of the reaction medium in the said solvothermal treatment zone adapted to obtain continuously, at the outlet of the said treatment zone solvothermal, a suspension comprising said phyllomineral synthetic particles.
- a process according to the invention makes it possible to obtain phyllomineral synthetic particles exhibiting remarkable structural and crystalline properties, and in particular structural properties that can be very close to those of natural phyllosilicates, and especially of a natural talc, continuously and in a surprisingly short duration, from a few seconds to a few minutes, while durations of several hours (typically of the order of 6 hours in WO2013 / 004979), or even several days, a priori incompatible with continuous implementation, were until now considered necessary to achieve a transformation sufficient of a reaction medium comprising a liquid medium containing said stoichiometric proportions of said chemical elements constituting said phyllomineral synthetic particles.
- a process according to the invention also makes it possible to prepare phyllosilicate particles whose properties and characteristics can be finely adjusted, in particular as a function of the duration of the solvothermal treatment (residence time), and with a solvothermal treatment at reduced temperatures, considered until now as insufficient.
- said phyllomineral synthetic particles comprise 4 silicon and / or germanium atoms for 3 atoms of said metal M, that is to say that they have the stoichiometry of talc (ie 4 silicon atoms for 3 magnesium atoms).
- said phyllomineral synthetic particles have a zero charge, and do not have a cationic deficit or cations arranged in the interfoliary spaces (inter-foliar cations).
- said phyllomineral synthetic particles are free of fluorine and other metals (or metal cations) than said metal M, said phyllomineral synthetic particles being especially free of lithium and calcium.
- the constituent chemical elements of said phyllomineral synthetic particles are therefore especially free of fluorine, lithium and calcium.
- the reaction medium circulating in the solvothermal treatment zone is devoid of fluorine and of lithium.
- continuous reactor any reactor for working with continuous flows and allowing a mixture of chemical species present in the reaction medium.
- any known continuous reactor can be used in a process according to the invention.
- said continuous reactor is a continuous reactor of constant volume.
- a continuous reactor chosen from the group consisting of piston reactors (or piston-type flow reactors) is used.
- Such a piston reactor is adapted so that all the chemical species of the reaction medium containing said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles introduced simultaneously into the solvothermal treatment zone have a same residence time in the solvothermal treatment zone.
- It may for example be tubular reactors in which the flow of the reaction medium is carried out in a laminar, turbulent or intermediate regime.
- any continuous cocurrent or countercurrent reactor with respect to the introduction and bringing into contact of the various compositions and / or liquid media contacted in a process according to the invention. invention.
- the solvothermal treatment zone of the reactor has at least one inlet adapted to allow the continuous introduction of at least one starting composition into said solvothermal treatment zone of the reactor, and at least one outlet through which said suspension is continuously recovered. comprising said phyllomineral synthetic particles.
- the reaction medium comprising a liquid medium and said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles present in the solvothermal treatment zone of the reactor is formed from at least one starting composition and is subjected to said solvothermal treatment, it is that is to say heating under pressure, so as to evolve spontaneously and continuously under the effect of this sole solvothermal treatment, until a suspension of phyllomineral synthetic particles continuously delivered at the exit of the treatment zone solvothermal reactor.
- the solvothermal treatment zone of the reactor comprises at least one conduit, called a reaction conduit, in which the reaction medium continuously circulates between at least one inlet adapted to allow the continuous introduction of at least one starting composition and at least one outlet through which the suspension comprising said phyllomineral synthetic particles is continuously recovered.
- Said reaction conduit may for example be in the form of a tube or a pipe whose diameter and shape are adapted to allow the circulation of the reaction medium between at least one inlet and at least one outlet of the treatment zone solvothermal.
- said solvothermal treatment is carried out by circulating said reaction medium in said reaction conduit, extending between at least one introduction inlet of at least one starting composition and at least one recovery outlet of said suspension of phyllomineral synthetic particles.
- the residence time of the reaction medium in the said solvothermal treatment zone of the reactor is therefore adjusted as a function of the internal volume of this reaction conduit between the inlet and the outlet, the flow rate and the density of the reaction medium circulating in this reaction conduit.
- the pressure of the solvothermal treatment is controlled by controlling the pressure prevailing inside said reaction duct, for example by means of a pressure regulator.
- the pressure is controlled so that the pressure prevailing inside said reaction duct is greater than the saturation vapor pressure of the liquid medium.
- the temperature of the solvothermal treatment is controlled by controlling the temperature of the reaction conduit.
- the temperature can be controlled by any appropriate means, for example by arranging said reaction conduit inside an enclosure in which the temperature is controlled.
- Other embodiments are possible, for example by providing said reaction conduit with a double jacket and controlling the temperature of the jacket.
- the temperature of the reaction medium in the reactor is adapted to allow said phyllomineral synthetic particles to be obtained, depending in particular on the pressure and the residence time during which the solvothermal treatment is carried out.
- said solvothermal treatment is carried out at a temperature of between 200 ° C. and 600 ° C., in particular between 250 ° C. and 450 ° C., and in particular between 350 ° C. and 400 ° C. .
- the reaction conduit extends inside an enclosure, and the temperature inside the enclosure is controlled at a value between 100 ° C. and 600 ° C. , especially between 200 ° C and 500 ° C, and more particularly between 350 ° C and 400 ° C.
- the temperature and the pressure of the solvothermal treatment are controlled by controlling the temperature of the reaction conduit and, respectively, the pressure prevailing inside said reaction conduit.
- the characteristics and the amount of liquid medium in the reaction medium are adapted to allow a continuous introduction of at least one starting composition into the solvothermal treatment zone of the reactor -particularly in the reaction conduit. and the circulation of the reaction medium continuously in the solvothermal treatment zone of the reactor, in particular in the reaction conduit, until an outlet thereof.
- the reaction medium has a suitable viscosity (by a suitable choice of the liquid medium and / or adjustment of the amount of liquid medium) so as to allow its continuous flow at the inlet of the solvothermal treatment zone of the reactor, in particular at the inlet of the reaction conduit, and the continuous circulation of the resulting reaction medium in the reactor, in particular in the reaction conduit.
- the viscosity of the reaction medium is also chosen so as to make it possible to obtain a suspension of phyllomineral synthetic particles at the outlet of the reactor that may flow from this outlet, at least in view of the pressure Power.
- the reaction medium may be formed from one or more starting composition (s).
- each starting composition comprises a liquid medium and at least a part of said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles.
- Each starting composition is chosen such that all of said starting compositions comprise said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles.
- reaction medium If the reaction medium is formed from a single starting composition, it must then comprise all the constituent chemical elements in stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles, that is to say the stoichiometric proportions of at least one chemical element selected from the group consisting of silicon and germanium, and at least one chemical element selected from the group of divalent and trivalent metals.
- the reaction medium is prepared continuously from at least a first starting composition comprising at least one mineral compound chosen from silicates and / or germanates, their solutions solids and mixtures thereof, and at least a second starting composition comprising at least one metal salt of at least one metal M (in particular a divalent or trivalent metal), said first and second compositions being brought into continuous contact with each other. upstream of at least one input of said solvothermal treatment zone.
- each starting composition comprising at least one mineral compound chosen from silicates and / or germanates, their solid solutions and mixtures thereof and / or at least one metal salt of at least one at least one metal M.
- the inventors have surprisingly found that it is it is possible to carry out a preparation of the reaction medium continuously, starting from several different starting compositions each containing at least a part of the constituent chemical elements necessary for the synthesis of the phyllomineral particles, whereas such a continuous implementation requires a priori significant dilutions. This dilution before and in the solvothermal treatment zone is generally presumed to interfere with obtaining such phyllomineral particles.
- the constituent chemical elements which, separately from each other, could not allow the formation of phyllomineral particles and would tend to form particles of a different structural and / or chemical nature, in fact allow such that they are brought into contact in a process according to the invention, obtaining phyllominéral synthetic particles, even in diluted medium.
- the concentration (relative to the volume of the liquid medium) of said constituent chemical elements of said phyllomineral synthetic particles introduced at the inlet of the solvothermal treatment zone of the reactor may in particular be between 10 mol / L and several mol / L, for example 10 mol / L or 1 mol / L.
- the reaction medium and each starting composition are at least partially hydrated (the solvothermal treatment of this reaction medium is then described as hydro-thermal treatment).
- said liquid medium is chosen from water, alcohols and mixtures thereof.
- said alcohols are chosen from linear or branched alcohols comprising less than 10 carbon atoms, in particular comprising less than 7 carbon atoms, in particular from methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, propylene glycol and ethylene glycol.
- the liquid medium of the starting composition and the liquid medium of the reaction medium may for example be prepared solely with water or with a mixture of water and at least one alcohol.
- the solvothermal treatment of the reaction medium is carried out in the solvothermal treatment zone of the reactor at a pressure suitable for obtaining said phyllo-mineral synthetic particles, particularly as a function of the temperature and the residence time during which the solvothermal treatment is carried out.
- said solvothermal treatment is carried out at a pressure of between 2 MPa and 50 MPa, in particular between 8 MPa and 40 MPa, and in particular between 22 MPa and 30 MPa.
- this pressure of the solvothermal treatment is controlled by adjusting the pressure inside the reaction conduit in which the reaction medium circulates.
- the pressure of the solvothermal treatment is controlled by a pressure regulator.
- the reaction conduit is prolonged after leaving the reactor (that is to say from an area in which the reaction conduit is maintained at a temperature corresponding to the temperature of the solvothermal reaction) by a portion provided with a device for regulating the pressure (such as for example a micro metric or needle valve or an automatic pressure regulator) to a value, called nominal pressure, at which the solvothermal treatment must be carried out.
- the reaction medium is introduced into the reaction conduit with a predetermined flow rate as a function of the residence time, for example using at least one flow pump (volumetric pump).
- This device makes it possible to control the pressure within the entire continuous synthesis device and in particular within the reactor. It also makes it possible to ensure a transition between the pressure in the reactor and the ambient pressure at the outlet of the continuous synthesis device, when the phyllomineral synthetic particles are recovered in suspension or after possible filtration.
- the duration of the solvothermal treatment is continuously adjusted by controlling the residence time of the reaction medium in said solvothermal treatment zone, in which it is subjected to the temperature and the pressure of the solvothermal treatment.
- the residence time of the reaction medium in the solvothermal treatment zone of the reactor is adapted to allow the continuous production of said synthetic particles phyllominoules, depending in particular on the temperature at which the solvothermal treatment is carried out.
- the reaction medium is circulated continuously in the solvothermal treatment zone of the reactor so that it has a residence time in the solvothermal treatment zone of less than 10 minutes, in particular less than 5 minutes. minutes, and more particularly less than 1 minute.
- the residence time of the reaction medium is determined from the volume of the reaction conduit (between the inlet and the outlet of this reaction conduit) in which the reaction medium, the flow rate imposed in the reaction conduit and the density of the reaction medium (the latter being dependent on the temperature and the pressure of the solvothermal treatment).
- the relationship between the volume flow rate (Q) and the residence time (t s ), the reactor volume (V r ), the density (p of the reaction medium at the inlet of the reactor and the density (p r ) of the reaction medium in the reactor is as follows:
- said reaction medium is introduced into the reactor -particularly into said reaction conduit-with a flow rate chosen to obtain the appropriate residence time.
- said solvothermal treatment is carried out under supercritical or subcritical conditions, and in particular homogeneous subcritical conditions.
- the temperature and the pressure at which the solvothermal treatment is carried out are chosen so that the reaction medium, and in particular the liquid medium which it comprises, is supercritical conditions.
- said solvothermal treatment is carried out under conditions of temperature and pressure such that the reaction medium - in particular its liquid medium - is under supercritical conditions.
- the critical point of the water (according to the phase diagram of the water) being located at 22.1 MPa and at 374 ° C., for example a hydrothermal treatment is carried out in the reactor at a temperature greater than 375 ° C and a pressure greater than 22.3MPa, so as to be in supercritical conditions.
- the invention applies to the preparation of any phyllo mineral particles obtainable by solvothermal treatment (heating and pressure) of a precursor gel comprising said stoichiometric proportions of said constituent chemical elements of said phyllomineral synthetic particles, the transformation of this precursor gel producing said phyllomineral particles at the end of the solvothermal treatment.
- the invention relates more particularly and advantageously to a process for preparing phyllosilicate particles belonging to the group consisting of lamellar silicates, lamellar germanates, lamellar germanosilicates and mixtures thereof.
- a precursor silico / germano-metallic hydrogel precursor is then used, and said solvothermal treatment is carried out in the form of a continuous hydrothermal treatment of this silico / germano-metallic hydrogel. precursor.
- said precursor gel is prepared by a co-precipitation reaction between at least one mineral compound, chosen from silicates, germanates, their solid solutions and mixtures thereof, and at least one metal salt of from minus a metal M (especially a divalent metal or tri valent).
- a method according to the invention thus makes it possible not only to carry out the solvothermal treatment of the precursor gel continuously but also the preparation of this precursor gel continuously.
- the co-precipitation reaction of the precursor gel is also rapid and thus makes it possible to carry out a synthesis of said phyllomineral synthetic particles continuously, allowing significant time savings.
- any compound comprising at least one silicon and / or germanium atom adapted to react in said co-precipitation reaction of said precursor gel is used as the inorganic compound.
- said mineral compound is chosen from the group consisting of sodium silicates and silicas (silicon dioxides).
- sodium metasilicate is used as the mineral compound.
- At least one dicarboxylate salt of formula is used as the metal salt of at least one metal M.
- R 1 is chosen from hydrogen (-H) and alkyl groups comprising less than 5 carbon atoms and
- said co-precipitation reaction is carried out in the presence of at least one carboxylate salt of formula R 2 -COOM 'in which:
- M 'de notes a metal selected from the group consisting of Na and K
- R 2 is chosen from H and the alkyl groups containing less than 5 carbon atoms.
- the groups R 1 and R 2 may be identical or different.
- the groups R 1 and R 2 are chosen from the group consisting of CH 3 -, CH 3 -CH 2 - and CH 3 -CH 2 -CH 2 -.
- the groups R 1 and R 2 are identical.
- the precursor gel used is a precursor hydrogel comprising:
- Water molecules can be further bound to the particles of this precursor hydrogel. They are water molecules adsorbed or physisorbed to the precursor hydrogel particles and not water molecules of constitution usually present in the interfoliar spaces of certain phyllosilicate particles.
- Another chemical formula for defining said precursor hydrogel is the following formula: (Si x Gei_ x ) 4M 3 Oii, nH 2 O, or also Si 4 M 3 Oii, nH 2 O with respect to a hydrogel silico-metallic precursor.
- Such a silico / germano-metallic precursor hydrogel can be obtained by a co-precipitation reaction between at least one mineral compound, selected from silicates, germanates, their solid solutions and mixtures thereof, and at least one metal salt of at least one divalent metal M.
- said solvothermal treatment is carried out, in particular a hydrothermal treatment, so as to obtain continuously (after leaving the reactor) a suspension comprising particles of phyllosilicate type 2: 1.
- said hydrothermal treatment is carried out so as to obtain continuously a suspension comprising phyllosilicate particles having the following chemical formula (II):
- Si means silicon
- Ge denotes germanium
- - M denotes at least one divalent metal having the formula Mg d Zn ⁇ Co ⁇ ⁇ j ⁇ Mn ⁇ Cu ⁇ Ni ⁇ Fe / Cr ⁇ j; each y (i) representing a
- x is a real number of the interval [0; 1].
- precursor gels comprising chemical elements in different proportions corresponding to the synthesis of other types of phyllominerals, for example phyllosilicates whose structure is of the TO type ( tetrahedron-octahedron) or TOTO type (tetrahedron-octahedron-tetrahedron octahedron), by analogy with 2: 1 phyllosilicates of T.O.T.
- a precursor gel making it possible to prepare phyllomeric synthetic particles of the T.O. type comprises, for example:
- the metal M may also designate a trivalent metal such as aluminum (Al) partially or totally substituted for said divalent metal.
- a precursor gel making it possible to prepare phyllomeric synthetic particles of T.O. or T.O.T. type. then will comprise 2 atoms of said trivalent metal (instead of 3 atoms of said divalent metal in order to respect the electrical neutrality).
- the precursor gel is continuously prepared immediately upstream of its introduction into the solvothermal treatment zone.
- a process according to the invention makes it possible to carry out, in a single step, continuously, on the one hand, the preparation of the precursor gel, and, on the other hand, the solvothermal treatment of the reaction medium making it possible to continuously obtain a suspension of synthetic particles. phyllominérales.
- the reaction medium, and in particular the precursor gel is prepared continuously, in particular by a co-precipitation reaction, starting from at least a first starting composition comprising at least a compound, said mineral compound, chosen from silicates and / or germanates, their solid solutions and their mixtures, and at least a second starting composition comprising at least one metal salt of at least one metal M chosen in the divalent metal and trivalent metal group, said first and second compositions being contacted continuously upstream of at least one inlet of said solvothermal treatment zone.
- the reactor comprises, upstream of the inlet of the reaction conduit, a first portion of conduit in which a first starting composition comprising each mineral compound is introduced continuously, and a second portion of conduit in which is introduced in continuously a second starting composition comprising each metal salt.
- the first starting composition is at least partially hydrated.
- the second starting composition is at least partially hydrated.
- the first starting composition is capable of flowing.
- the second starting composition is capable of flowing.
- said first starting composition and said second starting composition are liquid compositions fed continuously under liquid pressure, the liquid phase of each of these compositions being adapted so that their mixture forms said liquid medium of the medium. reaction.
- the first starting composition and the second starting composition are both solutions formed in said liquid medium.
- the first portion of the duct and the second portion of the duct meet upstream of the inlet of the solvothermal treatment zone -particularly upstream of the inlet of the reaction duct-in a third conduit portion connecting each of the first and second conduit portions and the inlet of the solvothermal treatment zone, the precursor gel forming (by co-precipitation) continuously in said third portion of conduit.
- the reactor thus has a third portion of duct extending downstream of the first duct portion and the second duct portion, said third duct portion extending to an inlet of the duct portion. reaction duct.
- said third portion of duct forms an intermediate portion between on the one hand, said first duct portion, the second duct portion and, on the other hand, the reaction duct (in which the solvothermal treatment is carried out. reaction medium for obtaining phyllominéral particles, and in particular phyllosilicatées particles).
- reaction medium for obtaining phyllominoul particles, and in particular phyllosilicatées particles In this third portion of conduit, each mineral compound and each metal salt are contacted to form the precursor gel by continuous co-precipitation.
- the flow rate of the precursor gel composition within the third portion of the duct and the length of the third portion of the duct are adapted to allow the continuous formation of the precursor gel upstream-especially immediately upstream of the inlet to the reactor-in particular the reaction line, that is to say before the solvothermal treatment.
- Preheating to a temperature above room temperature may optionally be provided in this third portion of conduit, before the entry of the reaction conduit.
- the suspension comprising the phyllominéral particles, and in particular phyllosilicatées is cooled downstream of its exit from the solvothermal treatment zone.
- Each duct (or portion of duct) of the continuous synthesis device used for carrying out a process according to the invention has dimensions adapted to allow a continuous flow of the various compositions (starting composition (s), reaction medium and obtained suspension comprising phyllomineral synthetic particles).
- Each duct and portion of duct may in particular have centifluidic dimensions (internal diameter greater than 1 cm) or millifluidic (internal diameter greater than 1 mm) or microfluidic (internal diameter less than 1 mm and in particular less than 750 ⁇ m).
- a reaction conduit is used having an internal diameter greater than 1 millimeter.
- the continuous reactor may have additional inputs located before the solvothermal treatment zone, at the level of the solvothermal treatment zone or after leaving the solvothermal treatment zone and before the exit of the suspension obtained.
- Such inputs may allow the introduction of a gas or a dense medium, for example a liquid (water or alcohol for example to control the proportion of liquid medium or to control the pH at any stage of the process) and / or a solid. It may for example also be grafting compositions using at least one water-soluble oxysilane having the formula (III):
- A denotes a group selected from methyl and hydrocarbon groups comprising at least one heteroatom; and R3, R4 and R5, are the same or different, and selected from hydrogen and linear alkyl groups comprising 1 to 3 carbon atom (s).
- Said oxysilane may for example be introduced before the solvothermal treatment zone and be a soluble trialkoxysilane in an aqueous medium and of the following formula:
- R3, R4 and R5 are identical or different, and selected from linear alkyl groups comprising 1 to 3 carbon atom (s),
- R7 is chosen from linear alkyl groups comprising 1 to 18 carbon atoms
- n is an integer from 1 to 5
- X " is an anion whose thermal stability is compatible with the temperature and residence time of the solvothermal treatment, and for example an anion in which X is selected from chlorine, iodine and bromine.
- compositions for functionalization of phyllomineral synthetic particles for example with magnetite particles, precipitation activators, catalysts for the precipitation reaction or transformation of at least one suspension starting composition comprising particles. phyllomineral synthetics, or even particles of silver.
- a suspension comprising particles of phyllosilicate type 2: 1 is obtained. More particularly, advantageously and according to the invention, a suspension comprising phyllosilicate particles in accordance with formula (II) is obtained.
- the phyllosilicate particles obtained by a process according to the invention exhibit, in X-ray diffraction, the following characteristic diffraction lines:
- the phyllosilicate particles obtained by a process according to the invention exhibit, in X-ray diffraction, the following characteristic diffraction lines:
- Such phyllosilicate particles are obtained in particular when using a precursor gel according to the above-mentioned formula (I).
- the suspension comprising phyllosilicate particles obtained by a process according to the invention can be dried by any powder drying technique.
- said synthetic particles obtained by freeze-drying are dried.
- the drying can also be carried out by means of an oven, for example at a temperature between 60 ° C. and 130 ° C., for 1 hour to 48 hours, under microwave irradiation, or else by atomization.
- the invention also relates to a method and a composition that can be obtained by a process according to the invention characterized in combination by all or some of the characteristics mentioned above or below.
- FIG. 1 is a schematic view of a device for preparing phyllomineral synthetic particles used in a process according to the invention
- FIGS. 2, 5, 7, 8, 9 represent X-ray diffractograms (RX) of phyllomineral particles obtained by the examples given below with a method according to the invention
- FIGS. 3, 4 and 6 show Fourier transform infrared absorption spectra of phyllomineral synthetic particles obtained by the examples given below with a method according to the invention
- FIGS. 10 and 11 are photographs of scanning electron microscopy with field effect of phyllomineral synthetic particles obtained in an example given below with a method according to the invention.
- a reactor 15 for the preparation of phyllomineral synthetic particles is used continuously (as illustrated in FIG. 1) comprising:
- a first aqueous solution comprising at least one mineral compound chosen from silicates, germanates, their solid solutions and their mixtures,
- a second portion 12 of conduit in which a second aqueous solution 21 is introduced comprising at least one metal salt of at least one metal M
- a third portion 13 of conduit disposed after the first conduit portion 11 and the second conduit portion 12 and extending to an inlet 9 of a reaction chamber 16, the first conduit portion 11 and the second portion 12 of conduit joining at a point 17 from which begins the third portion 13 of conduit,
- reaction conduit 14 extending from the inlet 9 into the reaction chamber 16, and after the third conduit portion 13.
- a peristaltic pump 18 continuously feeds the first portion 11 of conduit with the first aqueous solution contained in a tank 30 with stirring.
- a second peristaltic pump 19 continuously feeds the second portion 12 of conduit with the second aqueous solution 21 contained in a tank 31 with stirring.
- the reaction chamber 16 is an oven comprising a heating sleeve comprising ceramic material resistors.
- the reaction conduit 14 is in the general shape of a coil wound in multiple turns inside the heating sleeve, until it leaves the latter by an outlet 8 constituting the outlet of the chamber 16 of reaction.
- a co-precipitation reaction of a phyllomineral particle precursor gel takes place within the third portion 13 of the duct, upstream of the inlet 9, that is to say before the vo sol thermal treatment.
- the temperature of the precursor gel composition within the third conduit portion 13 is close to room temperature.
- the length of the third portion 13 of conduit may be surprisingly short, of the order of a few centimeters, and is for example between 10cm and 20cm. In the examples, this length is of the order of 15 cm.
- the residence time in the third portion 13 of the duct (between the point 17 and the inlet 9 of the chamber 16 of reaction) is also very reduced and can be less than 5 minutes, especially less than 1 minute or even less at 30 seconds.
- the total time for preparing phyllomineral synthetic particles by a process according to the invention is therefore less than 15 minutes, and in particular less than 10 minutes or even less than 5 minutes or of the order of one minute.
- a pressure regulator 2 is disposed downstream of the reaction chamber 16 in connection with a fifth portion 10 of conduit extending from the outlet 8 of the reaction conduit 14 and the reaction vessel 16 to a container 25. in which a suspension comprising the phyllomineral synthetic particles obtained is recovered.
- valve 32 interposed on the fifth portion 10 of conduit makes it possible to circulate the suspension obtained at the outlet 8 of the reaction conduit 14 in a circuit 33 which makes it possible to pass this suspension through a porous sinter 34 adapted to retain the particles and allow their recovery.
- the porous sinter 34 is immersed in an ice bucket 35 to cool the suspension leaving the reactor.
- valves 36 and 37 disposed on the branch circuit 33 are open.
- the porous sinter 34 is chosen so as to retain the phyllomineral particles synthesized by separating them from the liquid medium which carries them.
- the frit is for example made of 316L stainless steel, with a porosity of 50 ⁇ .
- the silico / germano-metallic gel can be prepared by a co-precipitation reaction involving, as reagent, at least one mineral compound comprising silicon and / or germanium at least one dicarboxylate salt of formula M (R COO) 2 (M denoting at least one divalent or trivalent metal and R 1 being chosen from H and alkyl groups containing less than 5 carbon atoms) in the presence of at least one salt carboxylate of formula R 2 COOM 'wherein M' denotes a metal selected from the group consisting of Na and K, and R 2 is selected from H and alkyl groups comprising less than five carbon atoms.
- the silico / germano-metallic gel is prepared by a co-precipitation reaction implemented from:
- salt (s) dicarboxylate prepared with one or more salt (s) dicarboxylate of formula M (R COO) 2 diluted in a carboxylic acid, such as acetic acid, and
- a silico / germano-metallic hydrogel comprising:
- hydrogel in an aqueous solution of carboxylate salt (s), said hydrogel being strongly hydrated (water molecules being bonded to the hydrogel particles without being water of constitution) and having a more or less gelatinous consistency.
- the hydrogel can also be recovered after centrifugation (for example between 3000 and 15000 rpm, for 5 to 60 minutes) and removal of the supernatant (solution of carboxylate salt (s)), optionally washing with demineralized water (for example two successive washes and centrifugations) and then drying, for example in an oven (60 ° C., 2 days), by lyophilization, by spray drying or by drying under irradiation of microwaves.
- demineralized water for example two successive washes and centrifugations
- the precursor gel may be prepared continuously as provided in the phyllomineral particle preparation device described above, or on the contrary beforehand, that is to say outside the device for preparing phyllomineral particles described above, and then introduced continuously as needed directly into the third portion 13 of conduit or directly to the inlet 9 of the conduit 14 reaction.
- the precursor hydrogel concentration in said precursor gel composition introduced at the inlet of the reaction chamber 16 is advantageously between 10 mol / l and several mol / l, for example of the order of 0.01 mol / l. It should be noted that this concentration is much lower than the concentrations used in the processes for the preparation of phyllomineral synthetic particles such as phyllosilicates of the state of the art. 3 / - Hydro-thermal treatment of said silico / germano-metallic hydrogel
- the precursor hydrogel of formula (I) above, dried or not, as previously obtained, is subjected to a hydrothermal treatment in the reaction conduit 14 when it enters the chamber 16 of reaction.
- Hydrothermal treatment is a solvothermal treatment which can in particular be carried out under supercritical or subcritical conditions, and in particular under homogeneous subcritical conditions.
- the temperature and the pressure at which this solvothermal treatment is carried out so that the precursor gel composition introduced at the inlet of the reactor, and in particular the solvent (s) it comprises is under supercritical conditions or under homogeneous subcritical conditions, i.e., above the liquid-gas equilibrium curve of the solvent, and so that the solvent is present in the liquid state and not in the form of a liquid-gas mixture or gas alone.
- a suspension comprising phyllosilicate mineral particles in an aqueous solution of carboxylate salt (s).
- the suspension obtained is recovered by filtration, for example by means of a ceramic sinter, or else by centrifugation (between 3000 and 15000 revolutions per minute, for 5 to 60 minutes) and then elimination of the supernatant.
- the supernatant solution contains salt (s) of formula R COOM 'and / or R 2 -COOM' and can be stored in order to recover this (s) salt (s) carboxylate (s) and (s) recycle.
- composition comprising recovered mineral particles may optionally be washed with water, in particular with distilled or osmosis water, for example by carrying out one or two washing / centrifugation cycles.
- composition comprising mineral particles recovered after the last centrifugation can then be dried:
- the phyllosilicate mineral particles contained in a talcose composition obtained by a process according to the invention have remarkable properties in terms of purity, crystallinity and thermal stability, and for an extremely short hydrothermal treatment duration (with respect to the duration hydrothermal treatment previously required in a known talcose compound preparation process), and without the need for subsequent anhydrous (annealing) heat treatment.
- talc In X-ray diffraction (RX), a natural talc such as talc from the ARNOLD mine (State of New York, USA) is known to exhibit the following characteristic diffraction lines (from the publication Ross M., Smith WL and Ashton WH, 1968, "Triclinic Talc and Associated Amphiboles Front Governor Mining District, New York, American Mineralogist," Volume 53, pages 751-769):
- FIGS. 2, 5, 7, 8, 9 show RX diffractograms of the particles obtained in the examples below, on each of which is represented the relative intensity of the signal (number of strokes per second) as a function of the angle of diffraction 2 ⁇ .
- the X-ray diffractograms represented were recorded on a CPS 120 device marketed by INEL (Artenay, France). It is a curved detector diffractometer allowing real-time detection over an angular range of 120 °.
- the acceleration voltage used is 40kV and the intensity of 25mA.
- the Bragg relation giving the structural equidistance is: (with the use of a cobalt anticathode).
- the diffraction lines that correspond respectively at the (003) and (060) planes have positions that coincide perfectly with those of the reference diffraction lines for natural talc.
- the size and particle size distribution of the phyllosilicate mineral particles that compose them were assessed by observation by scanning electron microscopy and field effect and by electron microscopy in transmission.
- a solution of magnesium acetate is prepared by adding 1.60817 g of magnesium acetate tetrahydrate (Mg (CH 3 COO) 2 , 4H 2 O) in 5 ml of acetic acid CH 3 COOH at 1 mol / l. and 245ml of distilled water.
- Mg (CH 3 COO) 2 , 4H 2 O magnesium acetate tetrahydrate
- a sodium metasilicate solution is prepared by adding 2,12136 g of sodium metasilicate pentahydrate (Na 2 OSiO 2 , 5H 2 O) in 250 ml of distilled water.
- the peristaltic pumps 18, 19 make it possible to bring the two solutions separately by steel ducts having an outer diameter of 1/8 of an inch (3.175 mm) and an internal diameter of 1.57 mm, and at a flow rate of 2 ml / min. each, a total flow of 4mL / min at point 17 where the mixture of two solutions intervene continuously, a few centimeters before the entry 9 of the conduit 14 reaction.
- the temperature in the chamber 16 is 400 ° C., and the pressure in the reaction conduit 14 is maintained (thanks to the pressure regulator 2) greater than 22 ⁇ MPa (between 25 MPa and 27 MPa), so that the reaction medium which circulates inside the reaction conduit 14 in the chamber 16 is under conditions above the critical point of water (374 ° C, 221bar).
- the precursor gel resulting from mixing and coprecipitation of the two solutions involved in the third portion 13 of conduit upstream of the inlet 9 of the reaction conduit 14, thus undergoes a hydro-thermal treatment in the enclosure 16 of reaction, which makes it possible to transform this precursor gel into a synthetic talc suspension.
- the residence time in the reaction conduit 14 between the inlet 9 and the outlet 8 is 23 seconds.
- the suspension resulting from the outlet 8 of the reactor 15 is a colloidal suspension of synthetic talc particles in a saline aqueous medium (sodium acetate). It has the appearance of a white milky composition that settles in several tens of minutes. This suspension is subjected to a centrifugation cycle (10 min at 8000 rpm). After centrifugation, on the one hand a talcose composition is recovered, and on the other hand a supernatant solution comprising in particular sodium acetate, the latter then being recoverable and optionally recycled.
- a talcose composition is recovered, and on the other hand a supernatant solution comprising in particular sodium acetate, the latter then being recoverable and optionally recycled.
- the recovered talcose composition is then subjected to two successive cycles of washing with demineralized water and centrifugation (10 min at 8000 rpm).
- the talcose composition recovered after centrifugation is finally dried in an oven at 60 ° C. for 12 hours.
- the X-ray diffractogram of the talc particles obtained according to the invention is represented by the curve 40 in FIG. 2.
- the X-ray diffractogram of this talcose composition has diffraction lines corresponding to the diffraction lines of the talc, and in particular the diffraction lines. following characteristics:
- Curve 40 is similar to that obtained by the method of
- Curve 44 in Fig. 2 is a comparative diffractogram of talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a 6-hour hydrothermal treatment, which are considered a reference.
- FIG. 3 represents the infrared absorption spectra of the particles obtained according to the invention in this example 1 (curve 37), by comparing them with the infrared absorption spectrum of the talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 1 hour (curve 38) and the infrared absorption spectrum of talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 2 hours (curve 39).
- FIG. 4 represents the infrared absorption spectra of the particles obtained according to the invention in this example 1 according to the invention in 23 s (curve 45), and of talc particles obtained by the method of WO2013 / 004979 at 300 ° C. with hydrothermal treatment of 3h (curve 46); talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 2 hours (curve 47); talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 1 hour (curve 48).
- Figs. 10 and 11 are SEM photographs illustrating phyllosilicate particles obtained in this example.
- Sub-micron talc particles visible in the photos of FIGS. 10 and 11 in a form in which the particles are agglomerated together) having a larger dimension of the order of 200A to 3000A, a thickness less than 100A corresponding to a few stacked sheets.
- a solution of magnesium acetate is prepared by adding 3.216 g of magnesium acetate tetrahydrate (Mg (CH 3 COO) 2 , 4H 2 O) in 10 ml of acetic acid CH 3 COOH at 1 mol / l and 490ml of distilled water.
- Mg (CH 3 COO) 2 , 4H 2 O magnesium acetate tetrahydrate
- a sodium metasilicate solution is prepared by adding 4.24284 g of sodium metasilicate pentahydrate (Na 2 OSiO 2 , 5H 2 O) in 500 ml of distilled water.
- the two solutions 20, 21 are fed by the pumps 18, 19 with a flow rate of 4 mL / min each, ie a total flow rate of 8 mL / min of reaction medium in the reaction line 14.
- the residence time in the reactor is 11 seconds.
- the other reaction conditions are identical to those of Example 1.
- the X-ray diffractogram of the talc particles obtained is represented by the curve 41 in FIG. 2.
- the X-ray diffractogram of this talcose composition has diffraction lines corresponding to the talc diffraction lines, and in particular the following characteristic diffraction lines.
- Curve 41 is similar to that obtained by the method of WO2013 / 004979 at 300 ° C but with a hydro-thermal treatment of 1 hour.
- a solution of magnesium acetate is prepared by adding 3.2165 g of magnesium acetate tetrahydrate (Mg (CH 3 COO) 2 , 4H 2 O) in 10 ml of acetic acid CH 3 COOH at 1 mol / l. and 490ml of distilled water.
- a sodium metasilicate solution is prepared by adding 4.24325 g of sodium metasilicate pentahydrate (Na 2 OSiO 2 , 5H 2 O) in 500 mL of distilled water.
- the ceramic sinter 34 is used at the outlet to separate the talc particles by filtering the suspension.
- the particles are recovered manually from the sinter (without washing or centrifugation) and then dried in an oven.
- the saline solution can be recovered at the sintered outlet and then dried to recover the salt.
- the remainder of the synthesized product can be recovered in the container 25, without passing through the sintered material. This part of the product is centrifuged, then washed / centrifuged twice. The talcose composition then recovered is then dried in an oven.
- the X-ray diffractograms of the talc particles obtained in this example 3 are represented by the curves 42 and 43 in FIG. 2.
- the curve 42 is obtained with the particles recovered by the sintered material.
- Curve 43 is obtained by the particles recovered by washing and centrifugation without the sinter.
- the X-ray diffractogram of the talcose composition represented by the curve 42 has diffraction lines corresponding to the talc diffraction lines, and in particular the following characteristic diffraction lines:
- the X-ray diffractogram of the talcose composition represented by the curve 43 has diffraction lines corresponding to the talc diffraction lines, and in particular the following characteristic diffraction lines: a plane (001) located at a distance of 10.54A;
- the curves 42 and 43 are similar to that obtained by the method of WO2013 / 004979 at 300 ° C. but with a hydrothermal treatment of 2 hours.
- FIG. 5 compares the RX diffractograms of the particles obtained in Example 1 according to the invention in 23s (curve 53), and of talc particles obtained by the method of WO2013 / 004979 at 300 ° C. with a hydrothermal treatment of 3h ( curve 54); particles obtained on the sinter in Example 3 according to the invention in 23s (curve 55) and talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 2 hours (curve 56); particles obtained in Example 2 according to the invention in I ls (curve 57) and talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 1 hour (curve 58).
- FIG. 6 compares infrared absorption spectra of particles obtained according to the invention in example 1 (curve 62), in example 2 (curve 63), and in example 3 (curve 64 for those obtained at from the sintered curve 65 for those obtained out of the sinter).
- a solution of magnesium acetate is prepared by adding 3.2165 g of magnesium acetate tetrahydrate (Mg (CH 3 COO) 2 , 4H 2 O) in 10 mL of acetic acid CH 3 COOH at 1 mol / L and 490ml of distilled water.
- Mg (CH 3 COO) 2 , 4H 2 O magnesium acetate tetrahydrate
- a sodium metasilicate solution is prepared by adding 4.24325 g of sodium metasilicate pentahydrate (Na 2 OSiO 2 , 5H 2 O) in 500 mL of distilled water.
- the X-ray diffractograms of the phyllosilicate particles obtained are represented by the curves 72, 73 and 74, respectively in FIG. 7.
- the curve 72 corresponds to the temperature of 350 ° C.
- the curve 73 corresponds to the temperature of 375 ° C.
- the curve 74 corresponds to the temperature of 400 ° C (similar to that of Example 1).
- the curves 72 and 73 are almost identical.
- a process according to the invention also makes it possible to obtain phyllosilicate particles having the structure of a talc under homogeneous subcritical conditions.
- the structural characteristics of the particles are even better and as can be seen through the curve 74, the crystallinity of the particles obtained under these conditions is exceptional and similar to that of a natural talc.
- the X-ray diffractogram of the talcose composition represented by the curve 72 has diffraction lines corresponding to the talc diffraction lines, and in particular the following characteristic diffraction lines:
- the X-ray diffractogram of the talcose composition represented by the curve 73 has diffraction lines corresponding to the talc diffraction lines, and in particular the following characteristic diffraction lines:
- the X-ray diffractogram of the talcose composition represented by the curve 74 has diffraction lines corresponding to the talc diffraction lines, and in particular the following characteristic diffraction lines:
- FIG. 8 compares the X-ray diffractograms of the particles obtained in test 2 (at 375 ° C.) according to the invention (curve 80), and of talc particles obtained according to the protocol described by WO2013 / 004979 at 230 ° C. with a hydrothermal treatment of 6 hours (curve 81), and talc particles obtained by the method of WO2013 / 004979 at 300 ° C with a hydrothermal treatment of 1 hour (curve 82).
- FIG. 9 compares the RX diffractograms of the particles obtained in test 3 (at 400 ° C.) according to the invention (curve 90), and of talc particles obtained by the method of WO2013 / 004979 at 300 ° C. with a treatment hydro thermal 3 hours (curve 91).
- the average size of the elementary particles obtained in the examples above is generally less than 3000 A.
- the size of the particles can of course vary depending in particular on the residence time and the temperature in the hydrothermal treatment zone, an increase in the residence time allowing, for example, an increase in the size of the particles essentially in the plane (a, b). ) of the crystal lattice of the particles (i.e., the width and length of the particles).
- the above examples show that it is easy to precisely adjust the structural characteristics of the phyllosilicate particles obtained by modifying the residence time, that is to say the duration of the solvothermal treatment, and / or the temperature of the treatment. solvothermal.
- the invention can be the subject of many variants.
- it is possible to provide several main conduits arranged in parallel in the same reactor; it is possible to prepare the precursor gel (or particles corresponding to this precursor gel) in advance to be able to use it as needed to carry out the solvothermal treatment; the device making it possible to continuously apply the temperature and the pressure of the solvothermal treatment to the reaction medium initially constituted by the precursor gel may be the subject of various embodiments ...
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- Chemical Kinetics & Catalysis (AREA)
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FR1453334A FR3019813B1 (fr) | 2014-04-14 | 2014-04-14 | Procede de preparation de particules synthetiques phyllominerales en continu |
PCT/FR2015/050984 WO2015159006A1 (fr) | 2014-04-14 | 2015-04-13 | Procédé de préparation de particules synthétiques phyllominérales en continu |
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FR3062073B1 (fr) | 2017-01-25 | 2024-01-05 | Centre Nat Rech Scient | Materiaux hybrides organiques/inorganiques photoluminescents et procede pour leur preparation |
EP3421422A1 (fr) | 2017-06-26 | 2019-01-02 | Centre National De La Recherche Scientifique | Procédé de fabrication de nanoparticules de phosphate de métal par synthèse solvothermale sous- et supercritique et nanoparticules obtenues par ce procédé |
EP3502056A1 (fr) | 2017-12-22 | 2019-06-26 | Imertech Sas | Co-synthèse de phyllominéraux et particules métalliques, et produits obtenus |
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