CN111995373B - Glue solution for internal gelling process and preparation method and application thereof - Google Patents
Glue solution for internal gelling process and preparation method and application thereof Download PDFInfo
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- CN111995373B CN111995373B CN202010802636.3A CN202010802636A CN111995373B CN 111995373 B CN111995373 B CN 111995373B CN 202010802636 A CN202010802636 A CN 202010802636A CN 111995373 B CN111995373 B CN 111995373B
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- urea
- hexamethylenetetramine
- complexing agent
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- 239000003292 glue Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 104
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 52
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 52
- 239000004202 carbamide Substances 0.000 claims abstract description 49
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008139 complexing agent Substances 0.000 claims abstract description 40
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 38
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 98
- 239000011259 mixed solution Substances 0.000 claims description 46
- 239000004005 microsphere Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 15
- -1 uranyl ions Chemical class 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- 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 6
- 239000008103 glucose Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-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
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002584 ketoses Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical compound O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 claims 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229960004011 methenamine Drugs 0.000 description 45
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 13
- 229910052770 Uranium Inorganic materials 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 10
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000001879 gelation Methods 0.000 description 9
- 238000006243 chemical reaction Methods 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
- 229910000442 triuranium octoxide Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 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 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002739 metals Chemical class 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
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000439 uranium oxide Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 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
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- 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
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- 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
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- 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
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of ceramic forming, and particularly relates to glue solution for an internal gelling process, and a preparation method and application thereof. The glue solution comprises metal ions, hexamethylenetetramine and urea; it also comprises complexing agent acetylacetone or its derivative. The glue solution can keep good stability at normal temperature, prolong the storage time, simplify the devices and equipment of the internal gelling process, such as cooling equipment, reduce the production cost and realize the glue solution conveying and gelling dispersion of industrial large-scale production; and the formed gel has high strength, so that the condition that the gel is cracked or even chipped in subsequent treatment is avoided.
Description
Technical Field
The invention belongs to the technical field of ceramic forming, and particularly relates to glue solution for an internal gelling process, and a preparation method and application thereof.
Background
The internal gelation process is an advanced technology for preparing ceramic microspheres and is widely applied to the preparation of fuel cores and inert matrixes of high-temperature gas cooled reactors. The basic principle is as follows: dropping colloid liquid containing hexamethylenetetramine, urea and metal salt (such as zirconium, uranium, titanium, aluminum and other metals) into a hot organic medium, and quickly decomposing hexamethylenetetramine in the hot organic medium to generate ammonium hydroxide to precipitate metal ions so as to solidify colloid liquid gel.
However, at normal temperature, when the glue solution is stored for a long time, hexamethylenetetramine in the glue solution can be automatically decomposed to cause the pH value of the glue solution to rise, and gold is generatedThe metal ions will react with OH-The reaction further promotes the accelerated decomposition of hexamethylenetetramine, so that metal ions are subjected to precipitation reaction in advance, which is also the main reason that the existing glue solution has short storage time at normal temperature. The glue solution is unstable at normal temperature and even low temperature, so that the large-scale application of the internal gelation process is restricted.
CN104671797A discloses an internal gelation method for preparing ceramic microspheres at a stable gel liquid at normal temperature, which comprises the following steps of controlling the concentration of metal salt in the gel liquid to be 0.8-1.4mol/L and the molar ratio of the metal salt, hexamethylenetetramine and urea to be 1 (1.1-1.3): (0.3-0.7), the preparation and storage of the glue solution are realized at normal temperature. The essence is that the urea content is reduced to slow down the automatic decomposition of hexamethylene tetramine, so that the stability of the glue solution is improved.
However, in the internal gelation process, it is known that urea and hexamethylenetetramine act to increase the pH of the sol system by the decomposition of hexamethylenetetramine, so that metal ions are hydrolyzed to gel the sol, and that the urea-formaldehyde resin produced by the reaction of formaldehyde and urea, which are the decomposition products of hexamethylenetetramine, acts to support the gel, thereby increasing the strength of the gel beads. The urea concentration in the liquid cement obtained by CN104671797A is too low, so that the formed gel is relatively soft, and can crack or even break in subsequent treatment, thereby reducing the performance of the ceramic microspheres.
Disclosure of Invention
The first purpose of the invention is to provide a glue solution for an internal gelling process. The glue solution can keep good stability at normal temperature, prolong the storage time, simplify the device (cooling device) of the internal gelling process, reduce the production cost and realize the glue solution conveying and gelling dispersion of industrial large-scale production; and the formed gel has high strength, thereby avoiding the situation that the gel is cracked or even cracked in the subsequent treatment, and providing guarantee for the industrial production of high-quality and high-yield ceramic microspheres.
The glue solution comprises metal ions, hexamethylenetetramine and urea; wherein the glue solution also comprises complexing agent acetylacetone or derivatives thereof.
The invention firstly proposes that acetylacetone or derivatives thereof as a specific complexing agent are added into the glue solution for the internal gelation process, and the promotion effect of metal ions on the decomposition of hexamethylenetetramine can be delayed through the specific complexing ability 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.
In order to obtain a glue solution with a better effect, an additive is also added into the second mixed solution.
The third purpose of the invention is to provide the application of the glue solution in the preparation of ceramic microspheres or powder materials by an internal gelation process.
The glue solution can be used for preparing oxide, carbide or nitride ceramic microspheres of metals such as U, Zr, Y, Fe, La, Mn, Zn, Pd, Ti and the like; and the obtained ceramic microspheres have uniform size and good sphericity.
The invention has the following beneficial effects:
the glue solution obtained by the invention can still keep good stability at normal temperature even in the presence of high-concentration urea and hexamethylene tetramine in high proportion, the storage time is prolonged, the device (cooling device) of the internal gelling process is simplified, the production cost is reduced, and the glue solution conveying and gelling dispersion of industrial large-scale production are realized; meanwhile, the limit requirements of the industrial production on the urea content in the existing glue solution and the proportion of the urea content to hexamethylenetetramine are reduced, and the large-scale application of the internal gelling process is really realized.
Drawings
FIG. 1 is a flow chart of a uranium gel microsphere prepared by adopting an internal gelation process in a glue solution according to example 3.
Fig. 2 is an SEM photograph of uranium oxide gel spheres prepared in example 4.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
EXAMPLE 1 preparation of a glue (without additives)
This embodiment provides a preparation of glue solution, including:
(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 acetylacetone.
EXAMPLE 2 preparation of a glue solution (containing additives)
This embodiment provides a preparation of glue solution, including:
(1) at room temperature, adding 3mol of hexamethylenetetramine and 2mol 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, 1mol/L of urea, 0.8mol/L of complexing agent acetylacetone and 0.8mol/L of additive glucose.
EXAMPLE 3 preparation of a glue solution (containing additives)
This embodiment provides a preparation of glue solution, including:
(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 acetylacetone and 0.8mol/L of additive glucose.
EXAMPLE 4 preparation of ceramic microspheres
The embodiment provides a preparation method of ceramic microspheres, which comprises the following steps:
(1) dispersing the glue solution obtained in the example 3 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;
(2) continuing aging the obtained gel spheres in silicone oil at 90 ℃ for 0.5-1 hour to obtain microspheres;
(3) cleaning the aged microspheres, specifically: four successive washes with Trichloroethylene (TCE) were used, 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 ℃, washing the microspheres with the deionized water after cooling until the conductivity of waste liquid is less than 10 mu S/cm, and finally washing the microspheres with propylene glycol methyl ether for four times, wherein each time lasts for at least 20 minutes;
(4) placing the washed microspheres for 1h at room temperature, and then placing the microspheres in a drying oven at 60-80 ℃ for drying for at least 12h to obtain dry spheres;
(5) 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. During the sintering process, the temperature rise is as slow as possible and is respectively 100 ℃, 300 ℃, 400 ℃ and 450 DEGThe temperature was maintained at 2 hours.
FIG. 1 is a flow chart of a uranium gel microsphere prepared by adopting an internal gelation process in a glue solution according to example 3.
Fig. 2 is an SEM photograph of uranium oxide gel spheres prepared in example 4.
Comparative example 1
The comparative example provides a preparation of a glue solution, comprising the following steps:
(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.
Comparative example 2
The comparative example provides a preparation of a glue solution, comprising 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, 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.
Comparative example 3
The dope was obtained by the steps (1) to (3) in example 1 using CN104671797A, except that the urea content in the step (1) was increased to 3 mol/L.
Effect verification
(1) Comparison of storage time of glue solution at Normal temperature
The glue solution obtained in the example 1 (the complexing agent is acetylacetone and does not contain additives) is stored for 1h at normal temperature;
the glue solution obtained in the example 2 (the complexing agent is acetylacetone, the additive is contained, and the molar ratio of urea to hexamethylenetetramine is 1: 1.5) is stored for 6 hours at normal temperature;
the glue solution (complexing agent is acetylacetone and contains additive) obtained in the embodiment 3 is stored for 6h at normal temperature;
the glue solution (the complexing agent is urea) obtained in the comparative example 1 can only stably exist for about 5 minutes at normal temperature to form gel, which shows that the complexation of urea and uranyl ions is too weak to be stored for a long time at normal temperature.
The glue solution (the complexing agent is citric acid) obtained in the comparative example 2 cannot form better gel even at higher temperature, which shows that the complexation of the uranyl ions by the citric acid is too strong to be beneficial to the gel.
The glue solution (without complexing agent and with the molar ratio of 1:1 between urea and hexamethylenetetramine) obtained in the comparative example 3 can form gel only after being stably existed for about 5 minutes at normal temperature, which shows that the existing glue solution can be ensured to be stable at normal temperature only by controlling the ratio of urea to hexamethylenetetramine.
(2) The influence of different glue solutions on the quality and the production process of the gel balls and the ceramic microspheres is investigated:
the strength of the gel balls obtained in example 4 is high, and cracking or even cracking rarely occurs in subsequent treatment; 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 influence of the glue solution obtained in example 1 on the quality of the gel balls and the ceramic microspheres and the production process is equivalent to that of example 4.
The strength of the gel ball prepared from the glue solution obtained in example 2 is lower than that of example 4, and the cracking and even the fragmentation in the subsequent treatment are relatively more, but the prepared ceramic microsphere is equivalent to that of example 4.
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 dope obtained in comparative example 2 hardly formed a gel, and thus ceramic microspheres could not be obtained.
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.
Example 4
Similar to example 1, the difference is: the molar ratio of the complexing agent to the metal ions is 0.1: 1.
Example 5
Similar to example 1, the difference is: the molar ratio of the complexing agent to the metal ions is 2: 1.
Example 6
Similar to example 1, the difference is: the complexing agent is ethyl acetoacetate.
Tests show that the glue solutions obtained in the above examples 4-6 can be stored for 40min, 6h and 5h at normal temperature.
The glue solutions obtained in examples 4 to 6 also produced ceramic microspheres according to the method described in example 4 with the same effect as example 4.
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 (10)
1. A glue solution for an internal gelling process, comprising: 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;
the molar ratio of the complexing agent to the metal ions is (0.1-2): 1;
the molar ratio of the urea to the hexamethylenetetramine is 1: (0.8-1);
the metal ions are uranyl ions;
the complexing agent is one or more of acetylacetone, ethyl acetoacetate or methyl acetoacetate.
2. The glue solution according to claim 1, wherein the molar ratio of the complexing agent to the metal ions is (0.5-2): 1.
3. the glue solution according to claim 2, comprising: the molar ratio of the complexing agent to the metal ions is (0.5-0.6): 1.
4. the glue solution according to claim 3, comprising: 1.3-1.5mol/L uranyl ion, 1.4-1.6mol/L hexamethylenetetramine, 1.4-1.6mol/L urea and 0.7-0.9mol/L acetylacetone.
5. The glue solution according to any one of claims 1 to 4, wherein the glue solution further comprises an additive;
the additive is selected from one or a combination of a plurality of aldehydes, ketones, aldoses and ketoses;
the molar ratio of the additive to the metal ions is (0.1-2): 1.
6. the glue solution of claim 5, wherein the additive is glucose or fructose.
7. The glue solution of claim 6, comprising: 1.3-1.5mol/L uranyl ions, 1.4-1.6mol/L hexamethylenetetramine, 1.4-1.6mol/L urea, 0.7-0.9mol/L acetylacetone and 0.7-0.9mol/L additive;
and the molar ratio of the complexing agent to the metal ions is (0.5-0.6): 1.
8. the process for preparing the glue solution of any one of claims 1 to 4, characterized by comprising:
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.
9. The process for preparing the glue solution of any one of claims 5 to 7, characterized by comprising:
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;
uniformly mixing the first mixed solution and the second mixed solution to form a glue solution;
wherein, an additive is also added into the second mixed solution.
10. Use of the glue solution according to any one of claims 1 to 7 in the preparation of ceramic microspheres or powder materials by an internal gelling process.
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| 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 |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
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