CN103011278B - Process for hydrothermally preparing zirconium oxychloride with low alkali consumption - Google Patents
Process for hydrothermally preparing zirconium oxychloride with low alkali consumption Download PDFInfo
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- CN103011278B CN103011278B CN201310010214.2A CN201310010214A CN103011278B CN 103011278 B CN103011278 B CN 103011278B CN 201310010214 A CN201310010214 A CN 201310010214A CN 103011278 B CN103011278 B CN 103011278B
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- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003513 alkali Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 122
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 76
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011734 sodium Substances 0.000 claims abstract description 30
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 24
- 239000004576 sand Substances 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- 229910052641 aegirine Inorganic materials 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 59
- 239000007788 liquid Substances 0.000 claims description 57
- 238000000926 separation method Methods 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000001556 precipitation Methods 0.000 claims description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- 229910006501 ZrSiO Inorganic materials 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 14
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 238000003672 processing method Methods 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- NYAWADGYOWCCLK-UHFFFAOYSA-N [Na].[Zr] Chemical compound [Na].[Zr] NYAWADGYOWCCLK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract 2
- 238000007500 overflow downdraw method Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 35
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 208000012826 adjustment disease Diseases 0.000 description 6
- 238000004537 pulping Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- -1 reodorant Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to a process for hydrothermally preparing zirconium oxychloride with low alkali consumption, and belongs to the technical field of compound preparation. The process comprises the following steps: stirring crushed superfine zircon sand (ZrSiO4) powder with a NaOH solution to prepare slurry, and then placing the slurry into an autoclave to perform hydrothermal reaction, and thus generating amorphous or crystalline acmite sodium zirconium silicate (Na2ZrSiO5) precursors under a condition with the temperature of 200-300 DEG C, the pressure of 3-7MPa and the reaction time of 3-12 hours; and then removing sodium by use of hydrochloric acid, removing silicon, purifying, concentrating and crystallizing to obtain zirconium oxychloride crystals. The process can be used for not only solving the problems such as high NaOH consumption, high energy consumption, recycling incapability of excessive alkali and serious pollution to the environment in the process of preparing the zirconium oxychloride from zircon sand by an alkali fusion method, but also realizing low impurity content and high purity of a zirconium oxychloride product obtained by the method.
Description
Technical field
The processing method that the present invention relates to low consumption buck hot preparation zirconium oxychloride, belongs to compound preparing technical field.
Background technology
Zirconium oxychloride is of many uses, can be used as the additive of the products such as the raw material of mordant dyes and mordant, fixative, reodorant, fire retardant, also can be used as stablizer, trade effluent coagulation treatment dose of oil field stratum earth etc., is also the important raw and processed materials of technical grade and high-purity zirconia, nanometer superfine zirconia.Nano zircite has the excellent physical and chemical performances such as high-melting-point, intensity be large, wear-resisting, anticorrosive, mainly for the manufacture of the field such as structural ceramics and functional materials; Can prepare the zirconium chemicalses such as zirconium carbonate, zirconium sulfate, zirconium nitrate, zirconium hydroxide taking zirconium oxychloride as raw material, be widely used in the fields such as pottery, chemical industry, light industry, electronics.Mainly adopt the domestic end of the sixties diacid two alkaline process to claim again " sulfuric acid process " to produce zirconium oxychloride, but adopt without enterprise now.Be zircon and caustic soda melting, after rinsing, silica removal and effect of sulfuric acid, then add ammoniacal liquor, obtain zirconium hydroxide precipitation, use dissolving with hydrochloric acid throw out, obtain zirconyl chloride solution, pulverize through evaporation concentration, crystallisation by cooling, crystal, make zirconium oxychloride crystal, concrete reaction formula is as follows:
ZrSiO
4+4NaOH→Na
2ZrO
3+Na
2SiO
3+2H
2O
Na
2ZrO
3+3H
2SO
4→Zr(SO
4)
2+Na
2SO
4+3H
2O
Zr(SO
4)
2+4NH
3·H
2O→Zr(OH)
4↓+2(NH
4)
2SO
4?
Zr(OH)
4+2HCl+5H
2O→ZrOCl
2+8H
2O
Mainly to adopt alkali fusion for the production of zirconium oxychloride at present, claim again a sour alkaline process, but still there is following defect in the method: temperature of reaction is not only up to 600-900 DEG C, energy consumption is high, and in the technique with zircon sand alkali fusion production zirconium oxychloride, one ton of zirconium oxychloride of every production need be used approximately 1.3 tons of solid caustic soda (solid NaOH), produce approximately 6 tons of useless white residues containing alkali waste water and 0.5 ton, because this processing method NaOH consumes large, the waste water serious environment pollution producing, thereby the U.S., Europe, the developed countries such as Japan reduce or stop producing zirconium oxychloride in succession, this also becomes the bottleneck that has restricted China's zirconium chemicals industry development.
Summary of the invention
The object of the invention is to solve zircon sand alkali fusion produces in zirconium oxychloride technique, NaOH consumes large, energy consumption is high, excessive alkali can not reclaim, cause the problems such as severe contamination to environment, a kind of processing method of low consumption buck hot preparation zirconium oxychloride is provided, and the zirconium oxychloride product foreign matter content being obtained by the method is low, and purity is high.
From alkali fusion sodium hydroxide decomposing zircon sand (ZrSiO
4) reaction known:
ZrSiO
4+ 4NaOH=Na
2zrO
3+ Na
2siO
3+ 2H
2o, the mol ratio that its desirable reaction conditions is sodium hydroxide and zircon sand is that 4:1(mass ratio is 0.87:1), Gu driven terms of mechanics is analyzed solid-contact reacts than solid-liquid or liquid-liquid reactions difficulty, the concentration that improves reagent in solid-solid reaction is the important factor that keeps dynamic response condition, experience shows that the reagent dosage of general solid-solid reaction all exceedes 50% of theoretical consumption, and the mol ratio of controlling sodium hydroxide and zircon sand is that 6:1(mass ratio is 1.3:1).Due to a sour alkaline process be mainly by high temperature alkali fuse melt-wash-remove sodium-acid decomposition-condensing crystal to obtain zirconium oxychloride, thereby excessive alkali can not reclaim, and all becomes waste water and waste liquid.The present invention reduces according to the surface tension of hydrosol under High Temperature High Pressure, and ionic product uprises, and water ionization constant increases, and brings out ion and promotes reaction, and sodium hydroxide is reagent and mineralizer, at ZrSiO
4+ 2 NaOH=Na
2zrSiO
5in reaction system, under hydro-thermal dynamic response condition, generate the zirconium silicate (Na of a kind of single-phase amorphous or acmite crystalline substance
2zrSiO
5) presoma, owing to being single-phase product, excessive aqueous sodium hydroxide solution can be utilized by secondary through solid-liquid separation, and in reaction system, the mol ratio of zirconium sodium is 1:2, greatly reduces the consumption of alkali.
For achieving the above object, the concrete technical scheme that the present invention adopts is as follows:
A processing method for low consumption buck hot preparation zirconium oxychloride, is characterized in that: by the zircon sand (ZrSiO after pulverizing
4) insert after ultrafine powder and the slurrying of NaOH solution stirring and in autoclave, carry out hydro-thermal reaction, under temperature 200-300 DEG C, the condition of pressure 3-7MPa, reaction times 3-12h, i.e. reaction generates the zirconium silicate (Na of amorphous or acmite crystalline substance
2zrSiO
5) presoma, and then through the de-sodium of hydrochloric acid, silica removal, purification, condensing crystal, prepare zirconium oxychloride crystal.
The related chemical equation of above-mentioned processing method is as follows:
ZrSiO
4+2?NaOH=?Na
2ZrSiO
5?↓+H
2O
Na
2ZrSiO
5+4HCl=H
2SiO
3?↓+ZrOCl
2+2NaCl+H
2O
ZrOCl
2+2H
2O=ZrO（OH）
2+2HCl
ZrO（OH）
2+2HCl=?ZrOCl
2+H
2O
The D 50 of described zircon sand ultrafine powder is 1-5 μ m, and preferably D50 is 2 μ m.
For promoting reaction efficiency and speed, the excessive 0.5-3 of described NaOH solution times, i.e. ZrSiO
4: NaOH mol ratio=1:3-6, preferably 1:4; Excessive NaOH solution continues reuse after processing by solid-liquid separation, to reach the object of low consumption alkali.
The concentration of described NaOH solution is controlled at 30%-50% by weight.
The preferred reaction conditions of described hydro-thermal reaction is: 250 DEG C of temperature, pressure 5MPa, reaction times 5h.
Described zirconium silicate (Na
2zrSiO
5) presoma comprises through the concrete technology step of the de-sodium of hydrochloric acid, silica removal, purification, condensing crystal:
A, solid-liquid separation are removed alkali excessive in reactant, and the alkali lye removing can utilize again;
B, after solid-liquid separation, by zirconium silicate (Na
2zrSiO
5) presoma fully dissolves with the aqueous hydrochloric acid of reaction mol ratio excessive 10-20%, obtains H
2siO
3, ZrOCl
2with the NaCl aqueous solution;
C, solid-liquid separation are removed the impurity such as silicic acid, ZrOCl
2become ZrO(OH at 100-120 DEG C by steaming acid hydrolysis with the NaCl aqueous solution)
2precipitation, controls the pH value 5-6 of the aqueous solution, then solid-liquid separation, washs and remove sodium ion, obtains ZrO(OH)
2filter cake;
The aqueous hydrochloric acid of D, the excessive 10-20% of use reaction mol ratio dissolves ZrO(OH)
2filter cake, again steams sour water at 100-120 DEG C after secondary filter and solves ZrO(OH)
2precipitation, solid-liquid separation again, fully washing precipitate, repeats 2-3 time with this, further removes the impurity in product;
E, by clean ZrO(OH)
2precipitated filter cakes fully reacts with the aqueous hydrochloric acid that reacts the excessive 40-60% of mol ratio, concentrated, and the zirconium content of controlling in solution is 150-180g/L, acidity is 5.5-8 g/L, be cooled to after room temperature, obtain zirconium oxychloride crystal through Crystallization Separation, remaining liquid can return to D step and steam acid hydrolysis again.
The concentration of described aqueous hydrochloric acid is G/G=15-25%.
The invention has the advantages that:
1, the present invention is by zircon sand (ZrSiO
4) with the hydro-thermal dynamic response under certain condition of NaOH solution, obtained the zirconium silicate (Na of a kind of single-phase amorphous or acmite crystalline substance
2zrSiO
5) presoma, owing to being single-phase product, excessive aqueous sodium hydroxide solution can be utilized by secondary through solid-liquid separation, and in reaction system, the mol ratio of zirconium sodium is 1:2, greatly reduces the consumption of alkali.
2, the present invention adopts excessive 0.5-3 NaOH solution and zircon sand (ZrSiO doubly
4) reaction, both promoting reaction efficiency and speed of response, excessive NaOH solution still can continue reuse after processing by solid-liquid separation simultaneously, has effectively reached the object of low consumption alkali.
3, the present invention is by presoma zirconium silicate (Na
2zrSiO
5) with hydrochloric acid reaction after solid-liquid separation, effectively realized the removal of silicon.
4, the ZrOCl generating in reaction process of the present invention
2with the NaCl aqueous solution, by steaming acid hydrolysis at 100-120 DEG C, and control the pH value 5-6 of the aqueous solution, guarantee ZrOCl
2fully be hydrolyzed into ZrO(OH)
2precipitation, washing has effectively realized removing of the impurity such as sodium after filtration.Since pH2 left and right, ZrOCl
2part is hydrolyzed into ZrO(OH)
2precipitation, pH5 left and right amount of hydrolysis reaches 98wt% left and right, the while is very high because the impurity such as Na, Fe, Al, Ca can not be hydrolyzed or be hydrolyzed pH value, therefore, by solid-liquid separation, can effectively remove sodium ion, obtains ZrO(OH)
2filter cake.
5, the present invention passes through ZrO(OH)
2filter cake and hydrochloric acid reaction are prepared into ZrOCl
2, and through 2-3 time repeatedly with hydrochloric acid reaction, steam acid hydrolysis, filter and wash, thereby further realized the removal of the impurity such as Na, Fe, Al, Ca.
6, the present invention is by the ZrO(OH obtaining through removal of impurities)
2while reaction with hydrochloric acid (HCl), on the one hand by solution acidity being controlled to 5.5-8 g/L, effectively prevent ZrOCl
2be hydrolyzed into ZrO(OH)
2; On the other hand by the content of zirconium in solution is controlled to 150-180g/L, thereby guarantee the zirconium oxychloride ZrOCl obtaining through Crystallization Separation
2product has higher yield.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
1, the zircon sand using in following examples, for the product that Australian Ai Luoka company produces, is processed into ultrafine powder by D 50 for 1-5 μ m, after testing, its component content (massfraction/%) as shown in Table 1:
The component content of table one zircon sand
2, the sodium hydroxide and the hydrochloric acid that in following examples, use are analytical pure, and in reaction system, water is distilled water.
Embodiment 1
Sodium hydroxide is mixed with to the aqueous solution of 50% weight ratio, gets 3000g by ZrSiO
4add the ultra-fine zircon sand 1146g of D50:1 μ m with NaOH mol ratio 1:6, after stirring pulping, insert in the autoclave of 5L, 300 DEG C of temperature of reaction, adjustment reaction pressure is 7MPa, reaction times 3h, removes excessive alkali by reactant solid-liquid separation, then the product of solid-liquid separation is fully dissolved with the aqueous hydrochloric acid of concentration 20%Wt, reaction mol ratio is excessive 15%, obtains reactant H
2siO
3, ZrOCl
2with the NaCl aqueous solution, solid-liquid separation is removed the impurity such as silicic acid, and remaining liquid steams sour water 120 DEG C of negative pressure and solves ZrO(OH)
2precipitation, controls pH5-6, and solid-liquid separation washing precipitation, remove sodium ion, obtains ZrO(OH)
2filter cake, fully dissolves with the aqueous hydrochloric acid of concentration 20%Wt again, and reaction mol ratio is excessive 15%, steams acid hydrolysis, reaction solution hydrolysis ZrO(OH after secondary filter)
2precipitation, the abundant washing precipitate of solid-liquid separation, repeats secondary with this, effectively removes impurity in product.By clean ZrO(OH)
2precipitated filter cakes fully reacts with the aqueous hydrochloric acid of concentration 20%Wt, and reaction mol ratio is excessive 60%, concentrated, controls solution acidity 8g/L, and zirconium 180 g/L in solution, are cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2o, wherein foreign matter content (massfraction/%) is: Fe
2o
30.001, SiO
20.003, Na
2o 0.003, TiO
20.001, CaO 0.001, is better than HG/T2772-2004 standard.
Embodiment 2
Sodium hydroxide is mixed with to the aqueous solution of 40% weight ratio, gets 3000g by ZrSiO
4add the ultra-fine zircon sand 917g of D50:1 μ m with NaOH mol ratio 1:6, after stirring pulping, insert in the autoclave of 5L, 250 DEG C of temperature of reaction, adjustment reaction pressure is 5MPa, reaction times 5h, removes excessive alkali by reactant solid-liquid separation, then the product of solid-liquid separation is fully dissolved with the aqueous hydrochloric acid of concentration 15%Wt, reaction mol ratio is excessive 10%, obtains reactant H
2siO
3, ZrOCl
2with the NaCl aqueous solution, solid-liquid separation is removed the impurity such as silicic acid, and remaining liquid steams sour water 100 DEG C of negative pressure and solves ZrO(OH)
2precipitation, controls pH5-6, and solid-liquid separation washing precipitation, remove sodium ion, obtains ZrO(OH)
2filter cake, fully dissolves with the aqueous hydrochloric acid of concentration 15%Wt again, and reaction mol ratio is excessive 10%, steams acid hydrolysis, reaction solution hydrolysis ZrO(OH after secondary filter)
2precipitation, the abundant washing precipitate of solid-liquid separation, repeats secondary with this, effectively removes impurity in product.By clean ZrO(OH)
2precipitated filter cakes fully reacts with the aqueous hydrochloric acid of concentration 15%Wt, and reaction mol ratio is excessive 40%, concentrated, controls solution acidity 8g/L, and zirconium 180 g/L in solution, are cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2o, wherein foreign matter content (massfraction)/% is: Fe
2o
30.0008, SiO
20.002, Na
2o 0.001, TiO
20.001, CaO 0.0006, is better than HG/T2772-2004 standard.
Embodiment 3
Sodium hydroxide is mixed with to the aqueous solution of 30% weight ratio, gets 3000g by ZrSiO
4add the ultra-fine zircon sand 1375g of D50:5 μ m with NaOH mol ratio 1:3, after stirring pulping, insert in the autoclave of 5L, 200 DEG C of temperature of reaction, adjustment reaction pressure is 3MPa, reaction times 12h, removes excessive alkali by reactant solid-liquid separation, then the product of solid-liquid separation is fully dissolved with the aqueous hydrochloric acid of concentration 20%Wt, reaction mol ratio is excessive 20%, obtains reactant H
2siO
3, ZrOCl
2with the NaCl aqueous solution, solid-liquid separation is removed the impurity such as silicic acid, and remaining liquid steams sour water 110 DEG C of negative pressure and solves ZrO(OH)
2precipitation, controls pH5-6, and solid-liquid separation washing precipitation, remove sodium ion, obtains ZrO(OH)
2filter cake, fully dissolves with the aqueous hydrochloric acid of concentration 20%Wt again, and reaction mol ratio is excessive 20%, steams acid hydrolysis, reaction solution hydrolysis ZrO(OH after secondary filter)
2precipitation, the abundant washing precipitate of solid-liquid separation, with this in triplicate, effectively removes impurity in product.By clean ZrO(OH)
2precipitated filter cakes fully reacts with the aqueous hydrochloric acid of concentration 20%Wt, and mol ratio is excessive 50%, concentrated, controls solution acidity 5.5g/L, and zirconium 160 g/L in solution, are cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2o, wherein foreign matter content (massfraction/%) is: Fe
2o
30.0003, SiO
20.001, Na
2o 0.001, TiO
20.001, CaO 0.0004, is better than HG/T2772-2004 standard.
Embodiment 4
Sodium hydroxide is mixed with to the aqueous solution of 35% weight ratio, gets 3000g by ZrSiO
4add the ultra-fine zircon sand 962g of D50:2 μ m with NaOH mol ratio 1:5, after stirring pulping, insert in the autoclave of 5L, 270 DEG C of temperature of reaction, adjustment reaction pressure is 4MPa, reaction times 10h, removes excessive alkali by reactant solid-liquid separation, then the product of solid-liquid separation is fully dissolved with the aqueous hydrochloric acid of concentration 15%Wt, reaction mol ratio is excessive 20%, obtains reactant H
2siO
3, ZrOCl
2with the NaCl aqueous solution, solid-liquid separation is removed the impurity such as silicic acid, and remaining liquid steams sour water 105 DEG C of negative pressure and solves ZrO(OH)
2precipitation, controls pH5-6, and solid-liquid separation washing precipitation, remove sodium ion, obtains ZrO(OH)
2filter cake, fully dissolves with the aqueous hydrochloric acid of concentration 15%Wt again, and reaction mol ratio is excessive 20%, steams acid hydrolysis, reaction solution hydrolysis ZrO(OH after secondary filter)
2precipitation, the abundant washing precipitate of solid-liquid separation, with this in triplicate, effectively removes impurity in product.By clean ZrO(OH)
2precipitated filter cakes fully reacts with the aqueous hydrochloric acid of concentration 15-25%Wt, and reaction mol ratio is excessive 45%, concentrated, controls solution acidity 6g/L, and the zirconium 165g/L in solution, is cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2o, wherein foreign matter content (massfraction/%) is: Fe
2o
30.0006, SiO
20.0025, Na
2o 0.001, TiO
20.001, CaO 0.0005, is better than HG/T2772-2004 standard.
Embodiment 5
Sodium hydroxide is mixed with to the aqueous solution of 45% weight ratio, gets 3000g by ZrSiO
4add the ultra-fine zircon sand 1547g of D50:3 μ m with NaOH mol ratio 1:4, after stirring pulping, insert in the autoclave of 5L, 230 DEG C of temperature of reaction, adjustment reaction pressure is 6MPa, reaction times 8h, removes excessive alkali by reactant solid-liquid separation, then the product of solid-liquid separation is fully dissolved with the aqueous hydrochloric acid of concentration 25%Wt, reaction mol ratio is excessive 20%, obtains reactant H
2siO
3, ZrOCl
2with the NaCl aqueous solution, solid-liquid separation is removed the impurity such as silicic acid, and remaining liquid steams sour water 115 DEG C of negative pressure and solves ZrO(OH)
2precipitation, controls pH5-6, and solid-liquid separation washing precipitation, remove sodium ion, obtains ZrO(OH)
2filter cake, fully dissolves with the aqueous hydrochloric acid of concentration 25%Wt again, and reaction mol ratio is excessive 20%, steams acid hydrolysis, reaction solution hydrolysis ZrO(OH after secondary filter)
2precipitation, the abundant washing precipitate of solid-liquid separation, with this in triplicate, effectively removes impurity in product.By clean ZrO(OH)
2precipitated filter cakes fully reacts with the aqueous hydrochloric acid of concentration 25%Wt, and reaction mol ratio is excessive 55%, concentrated, controls solution acidity 7.5g/L, and the zirconium 155g/L in solution, is cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2o, wherein foreign matter content (massfraction/%) is: Fe
2o
30.0006, SiO
20.001, Na
2o 0.0008, TiO
20.001, CaO 0.0003, is better than HG/T2772-2004 standard.
Embodiment 6
Sodium hydroxide is mixed with to the aqueous solution of 38% weight ratio, gets 3000g by ZrSiO
4add the ultra-fine zircon sand 1741g of D50:4 μ m with NaOH mol ratio 1:3, after stirring pulping, insert in the autoclave of 5L, 280 DEG C of temperature of reaction, adjustment reaction pressure is 5MPa, reaction times 10h, removes excessive alkali by reactant solid-liquid separation, then the product of solid-liquid separation is fully dissolved with the aqueous hydrochloric acid of concentration 25%Wt, reaction mol ratio is excessive 20%, obtains reactant H
2siO
3, ZrOCl
2with the NaCl aqueous solution, solid-liquid separation is removed the impurity such as silicic acid, and remaining liquid steams sour water 120 DEG C of negative pressure and solves ZrO(OH)
2precipitation, controls pH5-6, and solid-liquid separation washing precipitation, remove sodium ion, obtains ZrO(OH)
2filter cake, fully dissolves with the aqueous hydrochloric acid of concentration 25%Wt again, and reaction mol ratio is excessive 20%, steams acid hydrolysis, reaction solution hydrolysis ZrO(OH after secondary filter)
2precipitation, the abundant washing precipitate of solid-liquid separation, repeats secondary with this, effectively removes impurity in product.By clean ZrO(OH)
2precipitated filter cakes fully reacts with the aqueous hydrochloric acid of concentration 25%Wt, and reaction mol ratio is excessive 60%, concentrated, controls solution acidity 8g/L, and the zirconium 150g/L in solution, is cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2o, wherein foreign matter content (massfraction/%) is: Fe
2o
30.0008, SiO
20.0025, Na
2o 0.002, TiO
20.001, CaO 0.0006, is better than HG/T2772-2004 standard.
Claims (5)
1. a processing method for low consumption buck hot preparation zirconium oxychloride, is characterized in that: by the zircon sand (ZrSiO after pulverizing
4) insert after ultrafine powder and the slurrying of NaOH solution stirring and in autoclave, carry out hydro-thermal reaction, under temperature 200-300 DEG C, the condition of pressure 3-7MPa, reaction times 3-12h, i.e. reaction generates the zirconium silicate presoma of amorphous or acmite crystalline substance, and then through the de-sodium of hydrochloric acid, silica removal, purification, condensing crystal, prepare zirconium oxychloride crystal;
The D 50 of described zircon sand ultrafine powder is 1-5 μ m;
Described ZrSiO
4with the mol ratio of NaOH solution reaction be 1:3-6;
The concentration of described NaOH solution is controlled at 30%-50% by weight.
2. the processing method of low consumption buck hot preparation zirconium oxychloride according to claim 1, is characterized in that: the D50 of described zircon sand ultrafine powder is 2 μ m.
3. the processing method of low consumption buck hot preparation zirconium oxychloride according to claim 1, is characterized in that: described ZrSiO
4with the mol ratio of NaOH solution reaction be 1:4.
4. the processing method of low consumption buck hot preparation zirconium oxychloride according to claim 1, is characterized in that: the reaction conditions of described hydro-thermal reaction is: 250 DEG C of temperature, pressure 5MPa, reaction times 5h.
5. the processing method of low consumption buck hot preparation zirconium oxychloride according to claim 1, is characterized in that: described zirconium silicate presoma comprises through the concrete technology step of the de-sodium of hydrochloric acid, silica removal, purification, condensing crystal:
A, solid-liquid separation are removed alkali excessive in reactant;
B, after solid-liquid separation, by zirconium silicate (Na
2zrSiO
5) presoma fully dissolves with the aqueous hydrochloric acid of reaction mol ratio excessive 10-20%, obtains H
2siO
3, ZrOCl
2with the NaCl aqueous solution; The concentration of described aqueous hydrochloric acid is g/g=15-25%;
C, solid-liquid separation are removed silicic acid impurity, ZrOCl
2become ZrO(OH at 100-120 DEG C by steaming acid hydrolysis with the NaCl aqueous solution)
2precipitation, controls the pH value 5-6 of the aqueous solution, then solid-liquid separation, washs and remove sodium ion, obtains ZrO(OH)
2filter cake;
The aqueous hydrochloric acid of D, the excessive 10-20% of use reaction mol ratio dissolves ZrO(OH)
2filter cake, again steams sour water at 100-120 DEG C after secondary filter and solves ZrO(OH)
2precipitation, solid-liquid separation again, fully washing precipitate, repeats 2-3 time with this, further removes the impurity in product;
E, by clean ZrO(OH)
2precipitated filter cakes fully reacts with the aqueous hydrochloric acid that reacts the excessive 40-60% of mol ratio, concentrated, and the zirconium content of controlling in solution is 150-180g/L, acidity is 5.5-8 g/L, be cooled to after room temperature, obtain zirconium oxychloride crystal through Crystallization Separation, remaining liquid can return to D step and steam acid hydrolysis again.
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| CN104817110B (en) * | 2015-03-04 | 2016-08-24 | 郭志斌 | A kind of zircon sand fluidizing chlorination method produces high-purity zirconium oxychloride and the method for coproduction Silicon chloride. |
| CN108557879B (en) * | 2018-07-08 | 2020-04-28 | 景德镇陶瓷大学 | Preparation method of flaky partially stabilized zirconia |
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