CN103011278A - 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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- CN103011278A CN103011278A CN2013100102142A CN201310010214A CN103011278A CN 103011278 A CN103011278 A CN 103011278A CN 2013100102142 A CN2013100102142 A CN 2013100102142A CN 201310010214 A CN201310010214 A CN 201310010214A CN 103011278 A CN103011278 A CN 103011278A
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- zirconium oxychloride
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- hydrochloric acid
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- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 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 72
- 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
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 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
- 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 claims abstract description 6
- 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 61
- 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
- 229910006501 ZrSiO Inorganic materials 0.000 claims description 28
- 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
- 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 17
- 238000003672 processing method 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
- 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
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 claims 1
- 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
- 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
- 239000007787 solid Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 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
- 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
- 230000002950 deficient 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
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material 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
- Silicon Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (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 present invention relates to the processing method of low consumption buck hot preparation zirconium oxychloride, belong to the 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., also is 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 fields such as structural ceramics and functional materialss; Can prepare the zirconium chemicalses such as zirconium carbonate, zirconium sulfate, zirconium nitrate, zirconium hydroxide take 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 the rinsing, silica removal and effect of sulfuric acid, add again ammoniacal liquor, obtain the zirconium hydroxide precipitation, use the dissolving with hydrochloric acid throw out, obtain zirconyl chloride solution, pulverize through evaporation concentration, crystallisation by cooling, crystal, make the 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
Production for zirconium oxychloride mainly is to adopt alkali fusion at present, claim again a sour alkaline process, but still there is following defective in the method: temperature of reaction is not only up to 600-900 ℃, energy consumption is high, and producing with the zircon sand alkali fusion in the technique of 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 that contain alkali waste water and 0.5 ton, because this processing method NaOH consumes large, the waste water serious environment pollution that produces, thereby the U.S., Europe, the developed countries such as Japan reduce or stop to produce zirconium oxychloride in succession, and 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 the zircon sand alkali fusion produces in the 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 that is obtained by the method is low, and purity is high.
From alkali fusion sodium hydroxide decomposing zircon sand (ZrSiO
4) reaction as can be 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 the 4:1(mass ratio is 0.87:1), it is more difficult than solid-liquid or liquid-liquid reactions that driven terms of mechanics is analyzed solid-affixed tactile reaction, the concentration that improves reagent in solid-solid reaction is the important factor that keeps the dynamic response condition, experience shows that the reagent dosage of general solid-solid reaction all surpasses 50% of theoretical consumption, and the mol ratio of namely controlling sodium hydroxide and zircon sand is that the 6:1(mass ratio is 1.3:1).Since a sour alkaline process mainly be 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 the High Temperature High Pressure, and ionic product uprises, and water power increases from constant, bring out ion and promote reaction, sodium hydroxide be reagent be again mineralizer, at ZrSiO
4+ 2 NaOH=Na
2ZrSiO
5In the 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, 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 of the present invention's employing is as follows:
A kind of processing method of low consumption buck hot preparation zirconium oxychloride is characterized in that: the zircon sand (ZrSiO after will pulverizing
4) insert after ultrafine powder and the slurrying of NaOH solution stirring and carry out hydro-thermal reaction in the autoclave, under temperature 200-300 ℃, 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 take off sodium, silica removal, purification, condensing crystal through hydrochloric acid, prepare the 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 preferred D50 is 2 μ m.
Be to promote reaction efficiency and speed, the excessive 0.5-3 of described NaOH solution doubly, i.e. ZrSiO
4: NaOH mol ratio=1:3-6, preferred 1:4; Excessive NaOH solution continues reuse after processing by solid-liquid separation, to reach the purpose 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 ℃ of temperature, pressure 5MPa, reaction times 5h.
Described zirconium silicate (Na
2ZrSiO
5) presoma comprises through the concrete technology step that hydrochloric acid takes off sodium, silica removal, purification, condensing crystal:
A, solid-liquid separation are removed alkali excessive in the reactant, and the alkali lye that removes can utilize again;
B, after solid-liquid separation, with 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 ℃ by steaming acid hydrolysis with the NaCl aqueous solution)
2Precipitation, the pH value 5-6 of the control aqueous solution, sodium ion is removed in solid-liquid separation, washing again, obtains ZrO(OH)
2Filter cake;
The aqueous hydrochloric acid dissolving ZrO(OH of D, the excessive 10-20% of usefulness reaction mol ratio)
2Filter cake again steams sour water at 100-120 ℃ after the 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 the product;
E, with the ZrO(OH that cleans)
2Precipitated filter cakes fully reacts with the aqueous hydrochloric acid of the excessive 40-60% of reaction mol ratio, and is concentrated, and the zirconium content in the control solution is 150-180g/L, acidity is 5.5-8 g/L, after being cooled to room temperature, obtain the zirconium oxychloride crystal through Crystallization Separation, remaining liquid can return the 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, 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 having promoted reaction efficiency and speed of response, simultaneously excessive NaOH solution still can continue reuse after processing by solid-liquid separation, has effectively reached the purpose 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 that generates in the reaction process of the present invention
2With the NaCl aqueous solution, by steaming acid hydrolysis at 100-120 ℃, and the pH value 5-6 of the control aqueous solution, guaranteed ZrOCl
2Fully be hydrolyzed into ZrO(OH)
2Precipitation, washing has effectively realized removing of the impurity such as sodium after filtration.Because about pH2, ZrOCl
2Part is hydrolyzed into ZrO(OH)
2Precipitation, pH5 left and right sides amount of hydrolysis namely reaches about 98wt%, simultaneously because Na, Fe, that the impurity such as Al, Ca can not be hydrolyzed or be hydrolyzed pH value is very high, therefore passes through 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 ZrO(OH that will obtain through removal of impurities)
2With hydrochloric acid (HCl) when reacting, on the one hand by solution acidity being controlled at 5.5-8 g/L, effectively prevented ZrOCl
2Be hydrolyzed into ZrO(OH)
2Be controlled at 150-180g/L by the content with zirconium in the solution on the other hand, thereby guarantee the zirconium oxychloride ZrOCl that obtains through Crystallization Separation
2Product has higher yield.
Embodiment
The invention will be further described below in conjunction with embodiment.
1, the product that the zircon sand that uses in following examples is produced for Australian Ai Luoka company 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 use in following examples are analytical pure, and water is distilled water in the reaction system.
Embodiment 1
Sodium hydroxide is mixed with the aqueous solution of 50% weight ratio, gets 3000g by ZrSiO
4Ultra-fine zircon sand 1146g with NaOH mol ratio 1:6 adding D50:1 μ m, insert after the stirring pulping in the autoclave of 5L, 300 ℃ of temperature of reaction, the adjustment reaction pressure is 7MPa, reaction times 3h removes excessive alkali with the reactant solid-liquid separation, the product of the solid-liquid separation aqueous hydrochloric acid with concentration 20%Wt is fully dissolved again, the 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 ℃ of negative pressure and solves ZrO(OH)
2Precipitation, control pH5-6, sodium ion is removed in solid-liquid separation and washing precipitation, obtains ZrO(OH)
2Filter cake, the aqueous hydrochloric acid with concentration 20%Wt fully dissolves again, the reaction mol ratio is excessive 15%, steams acid hydrolysis after the secondary filter, reaction solution hydrolysis ZrO(OH)
2Precipitation, the abundant washing precipitate of solid-liquid separation repeats secondary with this, effectively removes impurity in the product.With the ZrO(OH that cleans)
2The aqueous hydrochloric acid of precipitated filter cakes and concentration 20%Wt fully reacts, and the reaction mol ratio is excessive 60%, and is concentrated, control solution acidity 8g/L, and zirconium 180 g/L in the solution are cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2O, wherein foreign matter content (massfraction/%) be: Fe
2O
30.001, SiO
20.003, Na
2O 0.003, TiO
20.001, CaO 0.001, be better than the HG/T2772-2004 standard.
Embodiment 2
Sodium hydroxide is mixed with the aqueous solution of 40% weight ratio, gets 3000g by ZrSiO
4Ultra-fine zircon sand 917g with NaOH mol ratio 1:6 adding D50:1 μ m, insert after the stirring pulping in the autoclave of 5L, 250 ℃ of temperature of reaction, the adjustment reaction pressure is 5MPa, reaction times 5h removes excessive alkali with the reactant solid-liquid separation, the product of the solid-liquid separation aqueous hydrochloric acid with concentration 15%Wt is fully dissolved again, the 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 ℃ of negative pressure and solves ZrO(OH)
2Precipitation, control pH5-6, sodium ion is removed in solid-liquid separation and washing precipitation, obtains ZrO(OH)
2Filter cake, the aqueous hydrochloric acid with concentration 15%Wt fully dissolves again, the reaction mol ratio is excessive 10%, steams acid hydrolysis after the secondary filter, reaction solution hydrolysis ZrO(OH)
2Precipitation, the abundant washing precipitate of solid-liquid separation repeats secondary with this, effectively removes impurity in the product.With the ZrO(OH that cleans)
2The aqueous hydrochloric acid of precipitated filter cakes and concentration 15%Wt fully reacts, and the reaction mol ratio is excessive 40%, and is concentrated, control solution acidity 8g/L, and zirconium 180 g/L in the 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, be better than the HG/T2772-2004 standard.
Embodiment 3
Sodium hydroxide is mixed with the aqueous solution of 30% weight ratio, gets 3000g by ZrSiO
4Ultra-fine zircon sand 1375g with NaOH mol ratio 1:3 adding D50:5 μ m, insert after the stirring pulping in the autoclave of 5L, 200 ℃ of temperature of reaction, the adjustment reaction pressure is 3MPa, reaction times 12h removes excessive alkali with the reactant solid-liquid separation, the product of the solid-liquid separation aqueous hydrochloric acid with concentration 20%Wt is fully dissolved again, the 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 ℃ of negative pressure and solves ZrO(OH)
2Precipitation, control pH5-6, sodium ion is removed in solid-liquid separation and washing precipitation, obtains ZrO(OH)
2Filter cake, the aqueous hydrochloric acid with concentration 20%Wt fully dissolves again, the reaction mol ratio is excessive 20%, steams acid hydrolysis after the secondary filter, reaction solution hydrolysis ZrO(OH)
2Precipitation, the abundant washing precipitate of solid-liquid separation with this triplicate, is effectively removed impurity in the product.With the ZrO(OH that cleans)
2The aqueous hydrochloric acid of precipitated filter cakes and concentration 20%Wt fully reacts, and mol ratio is excessive 50%, and is concentrated, control solution acidity 5.5g/L, and zirconium 160 g/L in the solution are cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2O, wherein foreign matter content (massfraction/%) be: Fe
2O
30.0003, SiO
20.001, Na
2O 0.001, TiO
20.001, CaO 0.0004, be better than the HG/T2772-2004 standard.
Embodiment 4
Sodium hydroxide is mixed with the aqueous solution of 35% weight ratio, gets 3000g by ZrSiO
4Ultra-fine zircon sand 962g with NaOH mol ratio 1:5 adding D50:2 μ m, insert after the stirring pulping in the autoclave of 5L, 270 ℃ of temperature of reaction, the adjustment reaction pressure is 4MPa, reaction times 10h removes excessive alkali with the reactant solid-liquid separation, the product of the solid-liquid separation aqueous hydrochloric acid with concentration 15%Wt is fully dissolved again, the 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 ℃ of negative pressure and solves ZrO(OH)
2Precipitation, control pH5-6, sodium ion is removed in solid-liquid separation and washing precipitation, obtains ZrO(OH)
2Filter cake, the aqueous hydrochloric acid with concentration 15%Wt fully dissolves again, the reaction mol ratio is excessive 20%, steams acid hydrolysis after the secondary filter, reaction solution hydrolysis ZrO(OH)
2Precipitation, the abundant washing precipitate of solid-liquid separation with this triplicate, is effectively removed impurity in the product.With the ZrO(OH that cleans)
2The aqueous hydrochloric acid of precipitated filter cakes and concentration 15-25%Wt fully reacts, and the reaction mol ratio is excessive 45%, and is concentrated, control solution acidity 6g/L, and the zirconium 165g/L in the solution is cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2O, wherein foreign matter content (massfraction/%) be: Fe
2O
30.0006, SiO
20.0025, Na
2O 0.001, TiO
20.001, CaO 0.0005, be better than the HG/T2772-2004 standard.
Embodiment 5
Sodium hydroxide is mixed with the aqueous solution of 45% weight ratio, gets 3000g by ZrSiO
4Ultra-fine zircon sand 1547g with NaOH mol ratio 1:4 adding D50:3 μ m, insert after the stirring pulping in the autoclave of 5L, 230 ℃ of temperature of reaction, the adjustment reaction pressure is 6MPa, reaction times 8h removes excessive alkali with the reactant solid-liquid separation, the product of the solid-liquid separation aqueous hydrochloric acid with concentration 25%Wt is fully dissolved again, the 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 ℃ of negative pressure and solves ZrO(OH)
2Precipitation, control pH5-6, sodium ion is removed in solid-liquid separation and washing precipitation, obtains ZrO(OH)
2Filter cake, the aqueous hydrochloric acid with concentration 25%Wt fully dissolves again, the reaction mol ratio is excessive 20%, steams acid hydrolysis after the secondary filter, reaction solution hydrolysis ZrO(OH)
2Precipitation, the abundant washing precipitate of solid-liquid separation with this triplicate, is effectively removed impurity in the product.With the ZrO(OH that cleans)
2The aqueous hydrochloric acid of precipitated filter cakes and concentration 25%Wt fully reacts, and the reaction mol ratio is excessive 55%, and is concentrated, control solution acidity 7.5g/L, and the zirconium 155g/L in the solution is cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2O, wherein foreign matter content (massfraction/%) be: Fe
2O
30.0006, SiO
20.001, Na
2O 0.0008, TiO
20.001, CaO 0.0003, be better than the HG/T2772-2004 standard.
Embodiment 6
Sodium hydroxide is mixed with the aqueous solution of 38% weight ratio, gets 3000g by ZrSiO
4Ultra-fine zircon sand 1741g with NaOH mol ratio 1:3 adding D50:4 μ m, insert after the stirring pulping in the autoclave of 5L, 280 ℃ of temperature of reaction, the adjustment reaction pressure is 5MPa, reaction times 10h removes excessive alkali with the reactant solid-liquid separation, the product of the solid-liquid separation aqueous hydrochloric acid with concentration 25%Wt is fully dissolved again, the 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 ℃ of negative pressure and solves ZrO(OH)
2Precipitation, control pH5-6, sodium ion is removed in solid-liquid separation and washing precipitation, obtains ZrO(OH)
2Filter cake, the aqueous hydrochloric acid with concentration 25%Wt fully dissolves again, the reaction mol ratio is excessive 20%, steams acid hydrolysis after the secondary filter, reaction solution hydrolysis ZrO(OH)
2Precipitation, the abundant washing precipitate of solid-liquid separation repeats secondary with this, effectively removes impurity in the product.With the ZrO(OH that cleans)
2The aqueous hydrochloric acid of precipitated filter cakes and concentration 25%Wt fully reacts, and the reaction mol ratio is excessive 60%, and is concentrated, control solution acidity 8g/L, and the zirconium 150g/L in the solution is cooled to room temperature, and Crystallization Separation goes out ZrOCl
2.8H
2O, wherein foreign matter content (massfraction/%) be: Fe
2O
30.0008, SiO
20.0025, Na
2O 0.002, TiO
20.001, CaO 0.0006, be better than the HG/T2772-2004 standard.
Claims (9)
1. the processing method of a low consumption buck hot preparation zirconium oxychloride is characterized in that: the zircon sand (ZrSiO after will pulverizing
4) insert after ultrafine powder and the slurrying of NaOH solution stirring and carry out hydro-thermal reaction in the autoclave, under temperature 200-300 ℃, 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 take off sodium, silica removal, purification, condensing crystal through hydrochloric acid, prepare the zirconium oxychloride crystal.
2. the processing method of described low consumption buck hot preparation zirconium oxychloride according to claim 1, it is characterized in that: the D 50 of described zircon sand ultrafine powder is 1-5 μ m.
3. the processing method of described low consumption buck hot preparation zirconium oxychloride according to claim 1 and 2, it is characterized in that: the D50 of described zircon sand ultrafine powder is 2 μ m.
4. the processing method of described 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 1:3-6.
5. it is characterized in that: described ZrSiO according to claim 1 or the processing method of 4 described low consumption buck hot preparation zirconium oxychlorides,
4With the mol ratio of NaOH solution reaction be 1:4.
6. the processing method of described low consumption buck hot preparation zirconium oxychloride according to claim 1, it is characterized in that: the concentration of described NaOH solution is controlled at 30%-50% by weight.
7. the processing method of described low consumption buck hot preparation zirconium oxychloride according to claim 1, it is characterized in that: the reaction conditions of described hydro-thermal reaction is: 250 ℃ of temperature, pressure 5MPa, reaction times 5h.
8. the processing method of described low consumption buck hot preparation zirconium oxychloride according to claim 1, it is characterized in that: described zirconium silicate presoma comprises through the concrete technology step that hydrochloric acid takes off sodium, silica removal, purification, condensing crystal:
A, solid-liquid separation are removed alkali excessive in the reactant;
B, after solid-liquid separation, with 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 silicic acid impurity, ZrOCl
2Become ZrO(OH at 100-120 ℃ by steaming acid hydrolysis with the NaCl aqueous solution)
2Precipitation, the pH value 5-6 of the control aqueous solution, sodium ion is removed in solid-liquid separation, washing again, obtains ZrO(OH)
2Filter cake;
The aqueous hydrochloric acid dissolving ZrO(OH of D, the excessive 10-20% of usefulness reaction mol ratio)
2Filter cake again steams sour water at 100-120 ℃ after the 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 the product;
E, with the ZrO(OH that cleans)
2Precipitated filter cakes fully reacts with the aqueous hydrochloric acid of the excessive 40-60% of reaction mol ratio, and is concentrated, and the zirconium content in the control solution is 150-180g/L, acidity is 5.5-8 g/L, after being cooled to room temperature, obtain the zirconium oxychloride crystal through Crystallization Separation, remaining liquid can return the D step and steam acid hydrolysis again.
9. the processing method of described low consumption buck hot preparation zirconium oxychloride according to claim 8, it is characterized in that: the concentration of described aqueous hydrochloric acid is G/G=15-25%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015089829A1 (en) * | 2013-12-20 | 2015-06-25 | 中国科学院过程工程研究所 | Method for preparing zirconium oxychloride from zircon sand |
| CN104817110A (en) * | 2015-03-04 | 2015-08-05 | 郭志斌 | Method for producing high-purity zirconium oxychloride and co-producing silicon tetrachloride through zircon sand boiling chlorination method |
| CN108557879A (en) * | 2018-07-08 | 2018-09-21 | 景德镇陶瓷大学 | A kind of preparation method of sheet partially stabilized zirconia |
| CN111362289A (en) * | 2020-03-19 | 2020-07-03 | 神华准能资源综合开发有限公司 | Preparation method of high-purity aluminum oxide |
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| CN1125195A (en) * | 1994-12-18 | 1996-06-26 | 常正亚 | Producing zirconium series products using non-crystallization purification method |
| CN1132181A (en) * | 1995-03-31 | 1996-10-02 | 广东工学院 | Method for prepn. of electronic grade ZrO2 by Zircon |
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2013
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| CN1125195A (en) * | 1994-12-18 | 1996-06-26 | 常正亚 | Producing zirconium series products using non-crystallization purification method |
| CN1132181A (en) * | 1995-03-31 | 1996-10-02 | 广东工学院 | Method for prepn. of electronic grade ZrO2 by Zircon |
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| MEOR YUSOFF MEOR SULAIMAN: "High Temperature Phase Transitions XRD Studies of Zirconia Produced from Different Sources", 《JOURNAL OF NUCLEAR AND RELATED TECHNOLOGIES》, vol. 2, no. 1, 30 June 2005 (2005-06-30), pages 11 - 18 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015089829A1 (en) * | 2013-12-20 | 2015-06-25 | 中国科学院过程工程研究所 | Method for preparing zirconium oxychloride from zircon sand |
| CN104817110A (en) * | 2015-03-04 | 2015-08-05 | 郭志斌 | Method for producing high-purity zirconium oxychloride and co-producing silicon tetrachloride through zircon sand boiling chlorination method |
| CN108557879A (en) * | 2018-07-08 | 2018-09-21 | 景德镇陶瓷大学 | A kind of preparation method of sheet partially stabilized zirconia |
| CN108557879B (en) * | 2018-07-08 | 2020-04-28 | 景德镇陶瓷大学 | Preparation method of flaky partially stabilized zirconia |
| CN111362289A (en) * | 2020-03-19 | 2020-07-03 | 神华准能资源综合开发有限公司 | Preparation method of high-purity aluminum oxide |
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|---|---|
| CN103011278B (en) | 2014-11-26 |
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