CN111960824B - Ceramic microsphere and preparation method thereof - Google Patents
Ceramic microsphere and preparation method thereof Download PDFInfo
- Publication number
- CN111960824B CN111960824B CN202010802646.7A CN202010802646A CN111960824B CN 111960824 B CN111960824 B CN 111960824B CN 202010802646 A CN202010802646 A CN 202010802646A CN 111960824 B CN111960824 B CN 111960824B
- Authority
- CN
- China
- Prior art keywords
- washing
- glue solution
- urea
- ceramic microspheres
- complexing agent
- 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.)
- Active
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 78
- 239000000919 ceramic Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 76
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000003292 glue Substances 0.000 claims abstract description 59
- 239000004202 carbamide Substances 0.000 claims abstract description 40
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 38
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 38
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000008139 complexing agent Substances 0.000 claims abstract description 32
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 19
- 239000002699 waste material Substances 0.000 claims description 15
- 229910052770 Uranium Inorganic materials 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 11
- 229920002545 silicone oil Polymers 0.000 claims description 10
- -1 uranium ions Chemical class 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000002045 lasting effect Effects 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000001879 gelation Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- 208000007976 Ketosis Diseases 0.000 claims description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000001323 aldoses Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002584 ketoses Chemical class 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 13
- 229920001807 Urea-formaldehyde Polymers 0.000 abstract description 8
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 abstract description 8
- 238000013467 fragmentation Methods 0.000 abstract description 5
- 238000006062 fragmentation reaction Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000008093 supporting effect Effects 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 63
- 239000011259 mixed solution Substances 0.000 description 38
- 229960004011 methenamine Drugs 0.000 description 33
- 238000002156 mixing Methods 0.000 description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 229910000442 triuranium octoxide Inorganic materials 0.000 description 7
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- WZECUPJJEIXUKY-UHFFFAOYSA-N [O-2].[O-2].[O-2].[U+6] Chemical compound [O-2].[O-2].[O-2].[U+6] WZECUPJJEIXUKY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- 229910000439 uranium oxide Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/51—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on compounds of actinides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/624—Sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62695—Granulation or pelletising
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63472—Condensation polymers of aldehydes or ketones
- C04B35/63484—Urea-formaldehyde condensation polymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/606—Drying
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6582—Hydrogen containing atmosphere
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of ceramic forming, and particularly relates to a ceramic microsphere and a preparation method thereof. The ceramic microspheres are obtained by a glue solution through an internal gelling process; wherein the glue solution comprises metal ions, hexamethylenetetramine and urea; the glue solution also comprises complexing agent acetylacetone or derivatives thereof. The addition of the complexing agent can prolong the stability of the glue solution at normal temperature, improve the urea content, generate more urea-formaldehyde resin and improve the supporting effect, thereby improving the strength of the gel ball and avoiding the cracking and even fragmentation in subsequent treatment. The ceramic microspheres obtained by the invention have the advantages of uniform size, good sphericity and no cracking on the surface, and the nozzle is not blocked in the preparation process, the yield is high, and the industrialized mass production can be realized. In addition, the invention adopts the nonionic surfactant to replace the organic solvent in the prior art, thereby not only reducing the wastewater treatment cost, but also greatly improving the production environment.
Description
Technical Field
The invention belongs to the technical field of ceramic forming, and particularly relates to a ceramic microsphere and a preparation method thereof.
Background
CN104671797A discloses an internal gelation method for preparing ceramic microspheres with stable colloidal liquid at normal temperature. In order to improve the normal temperature stability of the glue solution, the method controls the concentration of urea at a lower level, wherein the molar ratio of metal salt, hexamethylenetetramine and urea is 1 (1.1-1.3): (0.3-0.7).
However, because the concentration of urea is too low, the amount of urea-formaldehyde resin generated by the reaction of urea and hexamethylenetetramine decomposition product-formaldehyde is correspondingly reduced, and the overall supporting effect of urea-formaldehyde resin on the formed gel is correspondingly weak, so that for some metal ions (such as uranium), good gel balls are difficult to form by adopting the method, the yield of ceramic microspheres is reduced, and the large-scale application of the internal gelling process cannot be realized.
In addition, the method uses organic solvent harmful to human and environment for many times to wash the aged gel balls, thereby improving the cost of wastewater treatment.
Disclosure of Invention
The first purpose of the invention is to propose a novel ceramic microsphere.
The ceramic microspheres are obtained by glue solution through an internal gelling process; the glue solution comprises metal ions, hexamethylenetetramine and urea; wherein the glue solution also comprises complexing agent acetylacetone or derivatives thereof.
According to the invention, researches show that the complexing agent is added, so that the stability of the glue solution at normal temperature can be prolonged, the urea content can be increased, more urea-formaldehyde resin is generated, and the supporting effect is improved, so that the strength of the gel ball is improved, and the condition of cracking and even fragmentation in subsequent treatment is avoided. The ceramic microspheres obtained by the invention have the advantages of uniform size, good sphericity and no cracking on the surface, and the nozzle is not blocked in the preparation process, the yield is high, and the industrialized mass production can be realized.
Specifically, the invention firstly proposes that acetylacetone or derivatives thereof as a specific complexing agent are added into the glue solution for the internal gelling process, and the promotion effect of metal ions on the decomposition of hexamethylenetetramine can be delayed through the specific complexing capacity between the acetylacetone or the derivatives thereof and the metal ions. Research results show that specific complexing ability exists between acetylacetone or derivatives thereof and metal ions, the complexing ability can prevent the metal ions from further promoting accelerated decomposition of hexamethylenetetramine, improve stability, prolong storage time at normal temperature, and ensure normal operation of subsequent gelling and dispersion of glue solution, thereby providing a favorable basis for large-scale application of an internal gelling process and obtaining better technical effects. And the addition of the complexing agent can also reduce the limit of the existing internal gelation process on the molar ratio of urea to hexamethylenetetramine, and solve the problems that the existing glue solution has low gel strength due to too low urea content, and is easy to crack or even break in subsequent treatment.
Preferably, the complexing agent is one or more of acetylacetone, ethyl acetoacetate, methyl acetoacetate and the like; further preferably acetylacetone, which can form more suitable complexing ability with metal ions to further prevent the accelerated decomposition of hexamethylenetetramine and prolong the storage time at normal temperature.
Preferably, the molar ratio of the complexing agent to the metal ions is (0.1-2): 1, preferably (0.5-2): 1, can form more suitable complexing ability with metal ions to further prevent the accelerated decomposition of hexamethylenetetramine and prolong the storage time at normal temperature. Further, considering the production cost comprehensively, the molar ratio of the complexing agent to the metal ions is (0.5-0.6): 1.
preferably, the molar ratio of the urea to the hexamethylenetetramine is 1: (0.8-1).
We have found that in the reaction process of urea-formaldehyde resin production by the reaction of hexamethylenetetramine decomposition product-formaldehyde and urea, there are many technical factors (such as hexamethylenetetramine decomposition rate, formaldehyde volatilization rate and reaction degree of formaldehyde and urea) which affect the synthesis of urea-formaldehyde resin, and further affect the strength of gel beads. By controlling the molar ratio of the urea to the hexamethylenetetramine within a proper range, more urea-formaldehyde resin can be formed by the formaldehyde decomposed by the urea and the hexamethylenetetramine, so that the strength of the gel ball is increased.
Particularly, in the process of preparing ceramic microspheres by uranyl ions, because the structure of the uranyl ions is a linear structure formed by two oxygen atoms and one uranium ion (the two oxygen atoms already occupy the upper and lower sites of uranium), during hydrolysis, hydroxyl groups can only be combined with the uranium ions from a plane perpendicular to an O-U-O straight line, the structure of a body type polymer is difficult to form by bridging the hydroxyl groups like zirconium ions, and the formed gel is relatively soft, and cracks or even fragmentation can occur in subsequent treatment. The problem can be effectively solved by reasonably controlling the adding proportion of the urea and the hexamethylene tetramine.
In the glue solution, the concentration of the metal ions is 0.8-1.5mol/L, and the molar ratio of the metal ions to hexamethylene tetramine is 1: (1-1.2).
As one embodiment of the present invention, the glue solution includes: 0.8-1.5mol/L of metal ions, 0.8-1.8mol/L of hexamethylenetetramine, 0.8-1.8mol/L of urea and 0.1-1mol/L of complexing agent; and the molar ratio of the complexing agent to the metal ions is (0.5-0.6): 1, the molar ratio of the urea to the hexamethylenetetramine is 1: (0.8-1). Research shows that the glue solution has better stability at normal temperature and higher gel ball strength, and can effectively avoid the occurrence of cracking and even fragmentation in subsequent treatment.
The metal ions are ions of one or more of uranium, zirconium, yttrium, iron, lanthanum, manganese, zinc, palladium or titanium; preferably, the metal ion is selected from uranium ions. Research shows that compared with the existing uranium-containing glue solution, the uranium-containing glue solution has better stability at normal temperature and higher gel strength.
As one embodiment of the present invention, the glue solution includes: 1.3-1.5mol/L of uranium ions, 1.4-1.6mol/L of hexamethylenetetramine, 1.4-1.6mol/L of urea and 0.7-0.9mol/L of acetylacetone; and the molar ratio of the complexing agent to the metal ions is (0.5-0.6): 1; further preferably, the molar ratio of the urea to the hexamethylenetetramine is 1: (0.8-1).
In order to further improve the stability of the glue solution at normal temperature, the glue solution also comprises an additive.
The additive is one or a combination of more of aldehyde, ketone, aldose, ketose, secondary amine or arylamine, preferably fructose, glucose and the like; the molar ratio of the additive to the metal ions is (0.1-2): 1, the stability of the glue solution at normal temperature can be further improved.
As one embodiment of the present invention, the glue solution includes: 0.8-1.5mol/L of metal ions, 0.8-1.8mol/L of hexamethylenetetramine, 0.8-1.8mol/L of urea, 0.1-1mol/L of complexing agent and 0.1-1mol/L of additive; and the molar ratio of the complexing agent to the metal ions is (0.1-2): 1; further preferably, the molar ratio of the urea to the hexamethylenetetramine is 1: (0.8-1).
As one embodiment of the present invention, the glue solution includes: 1.3-1.5mol/L of uranium ions, 1.4-1.6mol/L of hexamethylenetetramine, 1.4-1.6mol/L of urea, 0.7-0.9mol/L of acetylacetone and 0.7-0.9mol/L of additives; and the molar ratio of the complexing agent to the metal ions is (0.5-0.6): 1; further preferably, the molar ratio of the urea to the hexamethylenetetramine is 1: (0.8-1).
The second purpose of the invention is to provide a preparation method of the glue solution, which comprises the following steps: mixing hexamethylenetetramine and urea in water at room temperature to form a first mixed solution; uniformly mixing metal salt, concentrated acid and a complexing agent in water to form a second mixed solution; and uniformly mixing the first mixed solution and the second mixed solution to form a glue solution.
In the first mixed solution, the concentration of hexamethylene tetramine is 1.6-3.2 mol/L, and the concentration of urea is 1.6-3.2 mol/L.
In the second mixed solution, the concentration of the metal salt is 1.2-3 mol/L, and the molar ratio of the complexing agent to the metal ions is (0.1-2): 1.
wherein the concentrated acid is an acid corresponding to the anion of the metal salt, for example, nitrate corresponds to concentrated nitric acid, and chloride corresponds to hydrochloric acid.
The volume ratio of the first mixed liquid to the second mixed liquid is 2: 3-3: 2.
The second purpose of the invention is to provide a preparation method of the ceramic microspheres.
The preparation method of the ceramic microspheres comprises the following steps: dispersing the glue solution into hot silicone oil to obtain gel balls, and aging, washing, drying and sintering to obtain ceramic microspheres; wherein the detergent used for washing is a nonionic surfactant.
The invention adopts the nonionic surfactant to replace the organic solvent (such as trichloroethylene and propylene glycol monomethyl ether) in the prior art to remove the silicone oil on the surface of the gel ball, thereby not only reducing the wastewater treatment cost, but also greatly improving the production environment.
Preferably, the nonionic surfactant is a tween or triton.
Preferably, when the nonionic surfactant is a tween, the concentration is 1 to 2 wt%.
Preferably, the washing temperature is 40-80 ℃, preferably 60-65 ℃, and the washing effect is better.
As one embodiment of the present invention, the washing process is as follows:
(1) continuously washing the aged gel spheres three times with a nonionic surfactant, each washing lasting at least 20 minutes;
(2) washing the gel balls obtained in the step (1) with 0.1-1mol/L ammonia water until the conductivity of the washing waste liquid is less than 600 mu S/cm; preferably 0.5-0.6mol/L ammonia water;
(3) washing the gel balls obtained in the step (2) by deionized water until the conductivity of the washing waste liquid is less than 10 mu S/cm;
(4) placing the gel balls obtained in the step (3) in a reaction kettle containing deionized water, preserving the heat at 200 ℃ for 3 hours, and cooling to room temperature;
(5) and (4) washing the gel balls obtained in the step (4) by using deionized water until the conductivity of the washing waste liquid is less than 10 mu S/cm.
Research shows that the washing times can be reduced, the procedure can be simplified and the efficiency can be improved by setting the washing procedure.
The drying is carried out in a vacuum drying mode. The vacuum drying conditions are as follows: 50-55 ℃ and is more than or equal to 12 hours under the vacuum condition. Research shows that under the condition, the drying effect is better, the efficiency is higher, and the obtained ceramic microspheres are not easy to crack.
Preferably, the sintering adopts a three-stage gradient sintering method, so that the ceramic microspheres have better compactness, more uniform surface size and better sphericity; the specific sintering system may be determined according to the compound.
Further preferably, for the metal ion uranium, the sintering comprises: roasting for 6-7h at 550-560 ℃ in air atmosphere; reducing for 6-7h at 750-760 ℃ in a hydrogen atmosphere; sintering at 1600 ℃ in an argon atmosphere until dense ceramic microspheres are formed.
Further preferably, in the sintering process, the heating rate is controlled to be 2-3 ℃/min, and the temperature is respectively kept at 100 ℃, 300 ℃, 400 ℃ and 450 ℃ for 2 hours, so that cracking of the ceramic microspheres caused by too fast heat release or absorption is avoided, and the high-quality ceramic microspheres are more favorably obtained.
The temperature of the silicone oil is 85-90 ℃. Research shows that under the temperature condition, the glue solution has better dispersibility, is quickly gelled and solidified into gel balls, and is more beneficial to improving the efficiency of the ceramic microspheres.
The aging conditions are as follows: 80-90 ℃ for 0.5-1 h.
In order to prepare the ceramic microspheres of metal carbide or nitride, one or a combination of several of macromolecular organic matters, carbon powder or surfactants can be added into the glue solution.
Furthermore, the macromolecular organic matters are mainly various sugars, starch or melamine and the like, and the addition amount is 50-500 g/L.
Furthermore, the high molecular organic matter is mainly water-soluble phenolic resin or epoxy resin and the like, and the addition amount is 20-200 g/L;
further, the adding amount of the carbon powder can be determined according to the stoichiometric ratio of the metal carbothermic reduction reaction, and the adding amount of the carbon powder is less than the amount of the carbon powder required by the metal carbothermic reduction.
Further, the surfactant may be Triton X-100, Tergitol XD, or the like.
The invention has the following beneficial effects:
according to the invention, the complexing agent is added, so that the stability of the glue solution at normal temperature can be prolonged, the urea content can be increased, more urea-formaldehyde resin is generated, and the supporting effect is improved, so that the strength of the gel ball is improved, and the condition of cracking and even fragmentation in subsequent treatment is avoided. The ceramic microspheres obtained by the invention have the advantages of uniform size, good sphericity and no cracking on the surface, and the nozzle is not blocked in the preparation process, the yield is high, and the industrialized mass production can be realized. In addition, the invention adopts the nonionic surfactant to replace organic solvents (such as trichloroethylene and propylene glycol monomethyl ether) in the prior art, thereby not only reducing the wastewater treatment cost, but also greatly improving the production environment.
Drawings
Fig. 1 is an SEM photograph of uranium oxide gel spheres prepared in example 1.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
It should be noted that the term "room temperature" used in the present invention means 20 to 25 ℃.
EXAMPLE 1 preparation of ceramic microspheres (additive-free glue solution)
The embodiment provides a preparation method of ceramic microspheres, which comprises the following steps:
(1) at room temperature, adding 3mol of hexamethylenetetramine and 3mol of urea into deionized water, and uniformly mixing to prepare 1L of mixed solution to form first mixed solution;
(2) dissolving triuranium octoxide in concentrated nitric acid at room temperature, and adding deionized water to prepare a 2.8M uranyl nitrate solution, wherein the pH value is 1.8-2.2;
taking 5ml of the uranyl nitrate solution, dripping 1ml of complexing agent acetylacetone into the solution, and uniformly mixing to form a second mixed solution;
(3) and uniformly mixing the first mixed solution and the second mixed solution according to the volume ratio of 1:1 to form a third mixed solution, namely the glue solution.
In the obtained glue solution: 1.4mol/L of metal ions, 1.5mol/L of hexamethylenetetramine, 1.5mol/L of urea and 0.8mol/L of complexing agent.
(4) Dispersing the obtained glue solution into 85-90 ℃ silicone oil by using a rack of an internal gelling process, wherein the glue solution droplets can keep a spherical shape under the action of surface tension to obtain gel spheres;
(5) continuing aging the obtained gel spheres in silicone oil at 90 ℃ for 0.5-1 hour to obtain microspheres;
(6) cleaning the aged microspheres, specifically:
three successive washes with 1 wt% tween 80 solution at 60 ℃ were carried out, each wash lasting at least 20 minutes;
then washing the microspheres with 0.5mol/L ammonia water until the conductivity of waste liquid generated by washing is less than 600 mu S/cm;
washing the microspheres with deionized water until the conductivity of the waste liquid obtained by washing is less than 10 mu S/cm;
then placing the microspheres in a reaction kettle, adding a certain amount of deionized water, preserving the heat at 200 ℃ for 3 hours, and cooling to room temperature;
washing the microspheres with deionized water until the conductivity of the waste liquid is less than 10 mu S/cm;
(7) placing the washed microspheres for 1h at room temperature, and then placing the microspheres in a vacuum drying oven at 50 ℃ for drying for at least 12h to obtain dry spheres;
(8) finally, roasting the obtained dry ball for 6 hours at 550 ℃ in air atmosphere to obtain U3O8Microspheres; then reducing for 6h at 750 ℃ in hydrogen atmosphere to obtain UO2Microspheres; finally sintering the mixture into compact UO at 1600 ℃ in argon atmosphere2And (3) microspheres.
In the sintering process, the heating rate is 2-3 ℃/min, and the temperature is respectively kept at 100 ℃, 300 ℃, 400 ℃ and 450 ℃ for 2 hours.
Fig. 1 is an SEM photograph of uranium oxide gel spheres prepared in example 1.
EXAMPLE 2A method for preparing ceramic microspheres (additive in glue solution)
The embodiment provides a preparation method of ceramic microspheres, which comprises the following steps:
(1) at room temperature, adding 3mol of hexamethylenetetramine and 3mol of urea into deionized water, and uniformly mixing to prepare 1L of mixed solution to form first mixed solution;
(2) dissolving triuranium octoxide in concentrated nitric acid at room temperature, and adding deionized water to prepare a 2.8M uranyl nitrate solution, wherein the pH value is 1.8-2.2;
dissolving 1.8g of glucose in 1ml of complexing agent acetylacetone, adding 5ml of uranyl nitrate solution into the solution, and uniformly mixing to form a second mixed solution;
(3) and uniformly mixing 6ml of the first mixed solution and the second mixed solution according to the volume ratio of 1:1 to form a third mixed solution, namely the glue solution.
In the obtained glue solution: 1.4mol/L of metal ions, 1.5mol/L of hexamethylenetetramine, 1.5mol/L of urea, 0.8mol/L of complexing agent and 0.8mol/L of glucose as an additive.
(4) Dispersing the obtained glue solution into 85-90 ℃ silicone oil by using a rack of an internal gelling process, wherein the glue solution droplets can keep a spherical shape under the action of surface tension to obtain gel spheres;
(5) continuing aging the obtained gel spheres in silicone oil at 90 ℃ for 0.5-1 hour to obtain microspheres;
(6) cleaning the aged microspheres, specifically:
three successive washes with 1 wt% tween 80 were carried out, each wash lasting at least 20 minutes;
then washing the microspheres with 0.5mol/L ammonia water until the conductivity of waste liquid generated by washing is less than 600 mu S/cm;
washing the microspheres with deionized water until the conductivity of the waste liquid obtained by washing is less than 10 mu S/cm;
then placing the microspheres in a reaction kettle, adding a certain amount of deionized water, preserving heat for 3 hours at 200 ℃, and cooling;
washing the microspheres with deionized water until the conductivity of the waste liquid is less than 10 mu S/cm;
(7) placing the washed microspheres for 1h at room temperature, and then placing the microspheres in a vacuum drying oven at 50 ℃ for drying for at least 12h to obtain dry spheres;
(8) finally, roasting the obtained dry ball for 6 hours at 550 ℃ in air atmosphere to obtain U3O8Microspheres; then reducing for 6h at 750 ℃ in hydrogen atmosphere to obtain UO2Microspheres; finally sintering the mixture into compact UO at 1600 ℃ in argon atmosphere2And (3) microspheres. In the sintering process, the heating rate is 2-3 ℃/min and is respectively 100 DEG CThe temperature is kept at 300 ℃, 400 ℃ and 450 ℃ for 2 hours respectively.
EXAMPLE 3 preparation of ceramic microspheres (glue solution containing glucose and carbon powder)
The embodiment provides a preparation method of ceramic microspheres, which comprises the following steps:
(1) at room temperature, adding 3mol of hexamethylenetetramine and 3mol of urea into deionized water, and uniformly mixing to prepare 1L of mixed solution to form first mixed solution;
(2) dissolving triuranium octoxide in concentrated nitric acid at room temperature, and adding deionized water to prepare a 2.8M uranyl nitrate solution, wherein the pH value is 1.8-2.2;
dissolving 1.8g of glucose in 1ml of complexing agent acetylacetone, adding 5ml of uranyl nitrate solution into the solution, and uniformly mixing to form a second mixed solution;
(3) uniformly mixing the 6ml of first mixed solution and the second mixed solution according to the volume ratio of 1:1 to form a third mixed solution;
(4) adding 0.17g of carbon powder into the mixed solution, and adding triton 100 to uniformly and stably disperse the carbon powder in the mixed solution to obtain the glue solution.
And (3) storing the prepared glue solution for 0.5-1h at room temperature, and performing ultrasonic dispersion for 5min for gelation dispersion.
In the glue solution finally obtained: 1.4mol/L of metal ions, 1.5mol/L of hexamethylenetetramine, 1.5mol/L of urea, 0.8mol/L of complexing agent, 0.8mol/L of additive glucose, 0.9-1 molar ratio of carbon powder to uranium ions and 1-2 pH value.
(4) Dispersing the glue solution obtained in the example 1 into silicone oil at 85-90 ℃ by using a rack of an internal gelling process, wherein the liquid drops of the glue solution can keep a spherical shape under the action of surface tension to obtain gel spheres;
(5) continuing aging the obtained gel spheres in silicone oil at 90 ℃ for 0.5-1 hour to obtain microspheres;
(6) cleaning the aged microspheres, specifically:
three successive washes with 1 wt% tween 80 were carried out, each wash lasting at least 20 minutes;
then washing the microspheres with 0.5mol/L ammonia water until the conductivity of waste liquid generated by washing is less than 600 mu S/cm;
washing the microspheres with deionized water until the conductivity of the waste liquid obtained by washing is less than 10 mu S/cm;
then placing the microspheres in a reaction kettle, adding a certain amount of deionized water, preserving heat for 3 hours at 200 ℃, and cooling;
washing the microspheres with deionized water until the conductivity of the waste liquid is less than 10 mu S/cm;
(7) placing the washed microspheres for 1h at room temperature, and then placing the microspheres in a vacuum drying oven at 50 ℃ for drying for at least 12h to obtain dry spheres;
(8) and finally sintering the obtained dry spheres in a high-purity nitrogen atmosphere at 1400 ℃ to obtain the compact UN microspheres. In the sintering process, the heating rate is 2 ℃/min, and the temperature is respectively kept at 100 ℃, 250 ℃, 360 ℃ and 550 ℃ for 2 hours.
Comparative example 1
The comparative example provides a preparation of ceramic microspheres, comprising the steps of:
(1) adding 3mol of hexamethylenetetramine into deionized water at room temperature, and uniformly mixing to prepare 1L of mixed solution to form first mixed solution;
(2) dissolving triuranium octoxide in concentrated nitric acid at room temperature, and adding deionized water to prepare a 2.8M uranyl nitrate solution, wherein the pH value is 1.8-2.2;
taking 5ml of the uranyl nitrate solution, adding 0.9g of complexing agent urea into the solution for dissolving and uniformly mixing to form a second mixed solution;
(3) and uniformly mixing 6ml of the first mixed solution and the second mixed solution according to the volume ratio of 1:1 to form a third mixed solution, namely the glue solution.
(4) Ceramic microspheres were prepared in the same manner as in example 3.
Comparative example 2
The comparative example provides a preparation of ceramic microspheres, comprising the steps of:
(1) at room temperature, adding 3mol of hexamethylenetetramine and 3mol of urea into deionized water, and uniformly mixing to prepare 1L of mixed solution to form first mixed solution;
(2) dissolving triuranium octoxide in concentrated nitric acid at room temperature, and adding deionized water to prepare a 2.8M uranyl nitrate solution, wherein the pH value is 1.8-2.2;
taking 5ml of the uranyl nitrate solution, adding 1.92g of complexing agent citric acid into the solution for dissolving and uniformly mixing to form a second mixed solution;
(3) and uniformly mixing 6ml of the first mixed solution and the second mixed solution according to the volume ratio of 1:1 to form a third mixed solution, namely the glue solution.
(4) Ceramic microspheres were prepared in the same manner as in example 3, but it was found that gel formation was difficult, and thus ceramic microspheres could not be prepared.
Comparative example 3
Adopting CN104671797A to prepare glue solution in steps (1) - (3) in example 1, wherein the difference is that the urea content in step (1) is increased to 3mol/L, and the metal ion is uranium; then the ceramic microspheres were prepared from the glue solution by the method described in example 3.
Effect verification
Inspecting the quality of the obtained gel balls and ceramic microspheres and the production process:
the strength of the gel balls obtained in the example 2 is high, and the cracking and even the cracking of the gel balls in the subsequent treatment are few; the obtained ceramic microspheres have the advantages of uniform size, good sphericity and no surface cracking, and the nozzle is not blocked in the preparation process, so that the industrial mass production can be realized.
The strength of the gel spheres obtained in example 1 is lower than that of example 2, and cracking and even cracking occur in the subsequent treatment, but the prepared ceramic microspheres are equivalent to those in example 2.
The glue solution obtained in the comparative example 1 has poor stability at room temperature, and is easy to block a nozzle during dispersion ball making, thus being not beneficial to industrialized mass production.
The glue solution obtained in the comparative example 3 is similar to that obtained in the comparative example 1, has poor stability at room temperature, is easy to block a nozzle during dispersion and ball making, and is not beneficial to industrial mass production.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (17)
1. A ceramic microsphere is prepared from a glue solution by an internal gelation process; the method is characterized in that the glue solution comprises metal ions, hexamethylenetetramine and urea; wherein, the glue solution also comprises complexing agent acetylacetone or derivatives thereof; the complexing agent is one or more of acetylacetone, ethyl acetoacetate or methyl acetoacetate;
the glue solution also comprises an additive; the additive is selected from one or more of aldehyde, ketone, aldose, ketose, secondary amine or arylamine.
2. The ceramic microspheres of claim 1, wherein the molar ratio of the complexing agent to the metal ions is (0.1-2): 1.
3. the ceramic microspheres of claim 2, wherein the additive is selected from the group consisting of glucose, fructose; the molar ratio of the additive to the metal ions is (0.1-2): 1.
4. the ceramic microspheres of claim 3, wherein the molar ratio of urea to hexamethylenetetramine is 1: (0.8-1).
5. The ceramic microspheres of claim 4, wherein the glue solution comprises: 0.8-1.5mol/L of metal ions, 0.8-1.8mol/L of hexamethylenetetramine, 0.8-1.8mol/L of urea and 0.1-1mol/L of complexing agent; and the molar ratio of the complexing agent to the metal ions is (0.5-0.6): 1.
6. the ceramic microspheres of claim 5, wherein the glue solution comprises: 1.3-1.5mol/L of uranium ions, 1.4-1.6mol/L of hexamethylenetetramine, 1.4-1.6mol/L of urea, 0.7-0.9mol/L of acetylacetone, 0.7-0.9mol/L of additives, and the mol ratio of the complexing agent to the metal ions is (0.5-0.6): 1.
7. a method of making the ceramic microspheres of any one of claims 1-6, comprising: dispersing the glue solution into hot silicone oil to obtain gel balls, and aging, washing, drying and sintering to obtain ceramic microspheres; the detergent adopted for washing is a nonionic surfactant.
8. The method according to claim 7, wherein the nonionic surfactant is a tween or triton.
9. The method according to claim 8, wherein the concentration of the nonionic surfactant is 1 to 2 wt% when it is a tween.
10. The method according to claim 9, wherein the washing temperature is 40 to 80 ℃.
11. The method of claim 10, wherein the washing temperature is 60 to 65 ℃.
12. The method of claim 11, wherein the washing is performed by:
(1) continuously washing the aged gel spheres three times with a nonionic surfactant, each washing lasting at least 20 minutes;
(2) washing the gel balls obtained in the step (1) with 0.1-1mol/L ammonia water until the conductivity of the washing waste liquid is less than 600 mu S/cm;
(3) washing the gel balls obtained in the step (2) by deionized water until the conductivity of the washing waste liquid is less than 10 mu S/cm;
(4) placing the gel balls obtained in the step (3) in a reaction kettle containing deionized water, preserving the heat at 200 ℃ for 3 hours, and cooling to room temperature;
(5) and (4) washing the gel balls obtained in the step (4) by using deionized water until the conductivity of the washing waste liquid is less than 10 mu S/cm.
13. The production method according to claim 12, wherein the concentration of the aqueous ammonia is 0.5 to 0.6 mol/L.
14. The production method according to any one of claims 7 to 13, wherein the sintering is performed by a three-stage gradient sintering method.
15. The method of manufacturing according to claim 14, wherein the sintering comprises: roasting for 6-7h at 550-560 ℃ in air atmosphere; reducing for 6-7h at 750-760 ℃ in a hydrogen atmosphere; sintering at 1600 ℃ in an argon atmosphere until dense ceramic microspheres are formed.
16. The method according to claim 15, wherein the temperature rise rate is controlled to be 2 to 3 ℃/min during the sintering process, and the temperature is maintained at 100 ℃, 300 ℃, 400 ℃ and 450 ℃ for 2 hours respectively.
17. The preparation method according to any one of claims 7 to 13 and 15 to 16, wherein one or a combination of several of macromolecular organic substances, carbon powder or surfactants is added into the glue solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010802646.7A CN111960824B (en) | 2020-08-11 | 2020-08-11 | Ceramic microsphere and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010802646.7A CN111960824B (en) | 2020-08-11 | 2020-08-11 | Ceramic microsphere and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111960824A CN111960824A (en) | 2020-11-20 |
| CN111960824B true CN111960824B (en) | 2021-09-24 |
Family
ID=73365265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010802646.7A Active CN111960824B (en) | 2020-08-11 | 2020-08-11 | Ceramic microsphere and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111960824B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102510846A (en) * | 2009-06-19 | 2012-06-20 | 法国电气公司 | Production of self-supporting ceramic materials having a reduced thickness and containing metal oxides |
| CN104003715A (en) * | 2014-05-19 | 2014-08-27 | 清华大学 | ZrC-ZrO2 composite ceramic microsphere and preparation method thereof |
| CN104671797A (en) * | 2015-02-09 | 2015-06-03 | 清华大学 | Internal gelation method for ceramic microspheres capable of keeping gel solution steady at normal temperature |
| CN105000887A (en) * | 2015-07-31 | 2015-10-28 | 清华大学 | Method for preparing ZrO2-ZrC composite ceramic microsphere by utilizing sucrose as carbon source |
| CN108840683A (en) * | 2018-07-05 | 2018-11-20 | 清华大学 | It is used to prepare the technique and zirconium nitride ceramic microsphere of zirconium nitride ceramic microsphere |
| CN111243770A (en) * | 2020-01-13 | 2020-06-05 | 清华大学 | Method for preparing monodisperse uranium dioxide microspheres |
| CN111470870A (en) * | 2020-03-26 | 2020-07-31 | 清华大学 | Composite ceramic microsphere and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8753534B2 (en) * | 2010-01-07 | 2014-06-17 | Jack L. Collins | Formulation and method for preparing gels comprising hydrous aluminum oxide |
-
2020
- 2020-08-11 CN CN202010802646.7A patent/CN111960824B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102510846A (en) * | 2009-06-19 | 2012-06-20 | 法国电气公司 | Production of self-supporting ceramic materials having a reduced thickness and containing metal oxides |
| CN104003715A (en) * | 2014-05-19 | 2014-08-27 | 清华大学 | ZrC-ZrO2 composite ceramic microsphere and preparation method thereof |
| CN104671797A (en) * | 2015-02-09 | 2015-06-03 | 清华大学 | Internal gelation method for ceramic microspheres capable of keeping gel solution steady at normal temperature |
| CN105000887A (en) * | 2015-07-31 | 2015-10-28 | 清华大学 | Method for preparing ZrO2-ZrC composite ceramic microsphere by utilizing sucrose as carbon source |
| CN108840683A (en) * | 2018-07-05 | 2018-11-20 | 清华大学 | It is used to prepare the technique and zirconium nitride ceramic microsphere of zirconium nitride ceramic microsphere |
| CN111243770A (en) * | 2020-01-13 | 2020-06-05 | 清华大学 | Method for preparing monodisperse uranium dioxide microspheres |
| CN111470870A (en) * | 2020-03-26 | 2020-07-31 | 清华大学 | Composite ceramic microsphere and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111960824A (en) | 2020-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106654278B (en) | Novel carbon sphere and preparation method and application thereof | |
| CN108054387B (en) | Preparation method of palladium-mesoporous silica hollow multi-core nano catalytic material | |
| CN102664275B (en) | Carbon-loaded kernel-shell copper-palladium-platinum catalyst for fuel battery and preparation method thereof | |
| CN108022758B (en) | Carbon-coated cerium dioxide hollow sphere and preparation method thereof | |
| CN104003715B (en) | ZrC-ZrO2Composite ceramics microsphere and preparation method thereof | |
| CN103252502B (en) | Hollow core shell structure Au@TiO2 nano-composite material and preparation method thereof | |
| CN114196970B (en) | Oxygen evolution catalyst and preparation method thereof | |
| CN111774050A (en) | Preparation method and application of supported catalyst for catalyzing dimethyl oxalate hydrogenation | |
| CN100484877C (en) | Preparation method for aluminium oxide with high thermal stability and large specific surface area | |
| CN104671797B (en) | Internal gelation method for ceramic microspheres capable of keeping gel solution steady at normal temperature | |
| CN109126760B (en) | High-dispersion nano metal oxide composite carbon material and preparation method and application thereof | |
| CN106111130B (en) | A kind of porous superhigh specific surface area IrO2Oxygen-separating catalyst and preparation method thereof | |
| CN102285686A (en) | Method for preparing iron-nitrogen codoped mesoporous nano titanium dioxide by fast sol-gel method | |
| CN101698609A (en) | Method for preparing spherical, monodisperse and single-size yttrium oxide nano-powder | |
| US20190326608A1 (en) | Palladium oxide catalyst for direct formic acid fuel cell and preparation method thereof | |
| CN112239223A (en) | Preparation method of rare earth oxide powder with large specific surface area | |
| CN111755707A (en) | Preparation method of platinum-cobalt alloy catalyst | |
| CN105810960A (en) | Composite material taking foam nickel as matrix and preparation method of composite material | |
| CN111960824B (en) | Ceramic microsphere and preparation method thereof | |
| CN109626423A (en) | A method of preparing poriferous titanium dioxide ball | |
| CN111496270A (en) | Method for preparing nano metal platinum particles | |
| RU2415707C2 (en) | Method of producing platinum catalysts | |
| CN114671452B (en) | Method for preparing massive cerium oxide aerogel by taking epoxy compound as gel accelerator | |
| CN111995373B (en) | Glue solution for internal gelling process and preparation method and application thereof | |
| CN102580778B (en) | Ruthenium-based ammonia synthesis catalyst with polyhydroxy ruthenium complex as precursor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |