CN1442369A - Crystallization technology in preparation of zirconium oxychloride and its crystalization equipment - Google Patents
Crystallization technology in preparation of zirconium oxychloride and its crystalization equipment Download PDFInfo
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- CN1442369A CN1442369A CN 03114137 CN03114137A CN1442369A CN 1442369 A CN1442369 A CN 1442369A CN 03114137 CN03114137 CN 03114137 CN 03114137 A CN03114137 A CN 03114137A CN 1442369 A CN1442369 A CN 1442369A
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Abstract
A crystallizing process in preparing zirconium chloride oxide includes such steps as alkali fusing, water washing, acid washing, acidifying, removing Si, concentrating, forced crystallizing and acid washing again. The said forced crystallizing includes loading the concentrated solution of zirconium chloride oxide in special crystallizer, stirring, adding cooling water and air for forcing cooling, and crystallizing. The said crystallizer has a crystallizing cavity with water cooling jacket, cooling water inlet and outlet and cooling air inlet and outlet.
Description
Technical field the present invention relates to the preparation method and the equipment thereof of rare metal salts, relates in particular to crystallization processes and crystallization apparatus thereof among a kind of basic zirconium chloride preparation method.
Background technology basic zirconium chloride (ZrOCl
28H
2O) be zirconates, the basic material of zirconium product, white or little yellow needle crystal is the main raw material of making other zirconium product, be widely used as additive, catalyzer and the water-resisting agent of weaving, leather, rubber, refractory materials and pottery, and metal conditioner, coating siccative.It is used and demand constantly increases.And the crystallization processes among the existing basic zirconium chloride preparation method; be in hydrochloric acid system, to carry out spontaneous nucleation; the time of finishing crystallisation process generally is 3～7; be subjected to directly influencing of amblent air temperature; and the crystal monoblock in the crystallizer tank is grown in together; must carry out the bulky crystal pulverizing process, operating environment also will be equipped with special labour protection.
Summary of the invention is the defective that remedies prior art, and the present invention proposes crystallization processes and the crystallization apparatus thereof among a kind of basic zirconium chloride preparation method, and the technical scheme of employing is as follows respectively:
Crystallization processes among this basic zirconium chloride preparation method is characterized in that:
Alkali fusion, washing, a pickling, acidifying, silica removal arranged successively, concentrate, forced crystallization and white picking operation.
Above-mentioned alkali fusion procedure is, according to weight ratio 1: 1.05～1.40, with zircon sand (ZrSiO
4) and sodium hydroxide (NaOH), carry out alkali fusion in the alkali fusion stove that the input temperature is 750～1050 ℃, generate water-fast sodium zirconate (Na
2ZrO
3) and water miscible water glass (Na
2SiO
3).
Above-mentioned washing step is, according to volume ratio 1: 3～5, resultant and water with alkali fusion procedure stir at normal temperatures, separating solid substances and water lotion, and repetitive operation 3～5 times makes sodium zirconate separate with water glass.
An above-mentioned pickling process is, according to volume ratio 1: 3～5, is 1～3 normal dilute hydrochloric acid with sodium zirconate and acidity, stir separating solid substances and pickle solution, repetitive operation 3～5 times at normal temperatures, zirconium in the sodium zirconate is separated with sodium, and sodium is retained in pickle solution.
Above-mentioned acidizing process is, the sodium zirconate that separates sodium is inserted in the acidification vessel, the control amount drops into the hydrochloric acid and the water of high density 27～30%, heated and boiled 10～30 minutes, make the sodium zirconate dissolving, generating acidity is 3～5 zirconium oxychloride solutions that equivalent, concentration are zirconium dioxide content 60～120 grams per liters.
Above-mentioned silica removal operation is, according to weight ratio 1: 0.01～1.00 ‰, the zirconium oxychloride solution with the flocculation agent input generates left standstill 20～40 hours at normal temperatures, and the silicon in the solution is separated with basic zirconium chloride, and siliceous deposits is at container bottom.
Above-mentioned enrichment process is, the zirconium oxychloride solution of removing silicon is inserted in the concentration response still, in the heating jacket of reactor, feed steam, it is 4.0～6.5 equivalents that the zirconium oxychloride solution heating is concentrated into acidity, concentration is zirconium dioxide content 160～240 grams per liters, carries out the crystalline requirement to meet.
Above-mentioned forced crystallization operation is, spissated zirconium oxychloride solution is inserted in the special-purpose crystallization apparatus, control stirring rake velocity of rotation is 20～30 rev/mins, stirs 10～20 hours, sends into water coolant and cooling air with zirconium oxychloride solution, by 100～120 ℃ of beginnings of temperature forced cooling, when temperature drops to 70～80 ℃, begin to generate the basic zirconium chloride crystal, when temperature continues to drop to 30 ℃, substantially finish crystallisation process, generate saccharoidal pin type basic zirconium chloride crystal and mother liquor.
Above-mentioned white picking operation is, pin type basic zirconium chloride crystal is soaked in 4.5～6.5 normal hydrochloric acid at normal temperatures, and soak time is 8～24 hours, inserts in the whizzer with 4.5～6.5 normal hydrochloric acid drip washing again, and centrifugation, to remove impurity iron wherein.
This basic zirconium chloride preparation method's further feature is:
Sodium hydroxide surrogate in the above-mentioned alkali fusion procedure can be a yellow soda ash, also can be lime carbonate, adopts the subsequent handling of surrogate, do corresponding adjustment.
Flocculation agent in the above-mentioned silica removal operation can be a polyacrylamide, also can be gelatin.
This basic zirconium chloride crystallization apparatus by the mixing component that comprises electric motor and support thereof, reducing transmission structure, stir shaft and stirring rake, and is provided with solution inlet to be crystallized and generates the crystallization cavity composition that crystal exports, and it is characterized in that:
Crystallization cavity also is provided with the water cooling chuck and the water coolant that is communicated with it is gone into, exported, and cooling air is gone into, exported.
The blade of stirring rake is an anchor formula blade.
Reducing transmission structure is the rack pinion transmission group, and control stirring rake velocity of rotation is 20～30 rev/mins.
The coating of stirring rake, the liner of crystallization cavity all adopt the heatproof high molecule material to make, and the liner of coupled pipeline, valve, matching used fluid reservoir also all adopts the heatproof high molecule material to make.
The further feature of this basic zirconium chloride crystallization apparatus is:
Above-mentioned heatproof high molecule material can be a polypropylene.
The further again feature of this basic zirconium chloride crystallization apparatus is:
The thickness of above-mentioned heatproof high molecule material is 4～10 millimeters.
The present invention's beneficial effect against existing technologies is, the crystallization processes of the inventive method is, behind enrichment process, then carries out the forced crystallization operation, also saved the bulky crystal pulverizing process, and simple flow is reasonable, generates the crystal homogeneous, and is superior in quality stable.Have the crystalline rate height, foreign matter content is few, and environmental pollution is light, the advantage that operational condition is good.The crystallization cavity of special-purpose crystallization apparatus of the present invention also is provided with the water cooling chuck and the water coolant that is communicated with it is gone into, exported, and cooling air goes into, exports, and the blade of stirring rake is an anchor formula blade, has to stir the advantage that stability is good.The crystal product of the inventive method can satisfy preferably as the requirement of making other zirconium product main raw material, can be widely used as additive, catalyzer and the water-resisting agent of fabric, leather, rubber, refractory materials and pottery, and metal conditioner, coating siccative.
Appended drawings is a crystallization apparatus structural representation of the present invention.
Embodiment
Crystallization processes among 1 one kinds of basic zirconium chloride preparation methods of embodiment
This crystallization processes has alkali fusion, washing, a pickling, acidifying, silica removal successively, concentrates, forced crystallization and white picking operation.
Above-mentioned alkali fusion procedure is, according to weight ratio 1: 1.15, with zircon sand and sodium hydroxide, drops in the alkali fusion stove of 900 ℃ of temperature and carries out alkali fusion, generates water-fast sodium zirconate and water miscible water glass.
Above-mentioned washing step is, according to volume ratio 1: 5, resultant and water with alkali fusion procedure stirred at normal temperatures, separating solid substances and water lotion, and repetitive operation 4 times makes sodium zirconate separate with water glass.
An above-mentioned pickling process is, according to volume ratio 1: 4.5, is 1.5 normal dilute hydrochloric acid with sodium zirconate and acidity, stir at normal temperatures, and separating solid substances and pickle solution, repetitive operation 5 times makes the zirconium in the sodium zirconate separate with sodium, and sodium is retained in pickle solution.
Above-mentioned acidizing process is, the sodium zirconate that separates sodium is inserted in the acidification vessel, and the control amount drops into the hydrochloric acid and the water of high density 28%, heated and boiled 15 minutes, make the sodium zirconate dissolving, generating acidity is 3.5 zirconium oxychloride solutions that equivalent, concentration are zirconium dioxide content 110 grams per liters.
Above-mentioned silica removal operation is, according to weight ratio 1: 0.1 ‰, the zirconium oxychloride solution with flocculation agent polyacrylamide input generates left standstill 24 hours at normal temperatures, and the silicon in the solution is separated with basic zirconium chloride, and siliceous deposits is at container bottom.
Above-mentioned enrichment process is, the zirconium oxychloride solution of removing silicon is inserted in the concentration response still, feed steam in the heating jacket of reactor, it is 5.8 equivalents that the zirconium oxychloride solution heating is concentrated into acidity, concentration is zirconium dioxide content 220 grams per liters, carries out the crystalline requirement to meet.
Above-mentioned forced crystallization operation is, spissated zirconium oxychloride solution is inserted in the special-purpose crystallization apparatus, control stirring rake velocity of rotation is 25 rev/mins, stirs 12 hours, sends into water coolant and cooling air with zirconium oxychloride solution, by 110 ℃ of beginnings of temperature forced cooling, when temperature drops to 75 ℃, begin to generate the basic zirconium chloride crystal, when temperature continues to drop to 30 ℃, substantially finish crystallisation process, generate saccharoidal pin type basic zirconium chloride crystal and mother liquor.
Above-mentioned white picking operation is, pin type basic zirconium chloride crystal is soaked in 6 normal hydrochloric acid at normal temperatures, and soak time is 12 hours, insert again in the whizzer with 6 normal hydrochloric acid drip washing, and centrifugation, to remove impurity iron wherein.
Finally prepd basic zirconium chloride finished product, detect through the feeler mechanism that country is assert, every quality index meets relevant criterion fully, and the content of all cpds is respectively: zirconium dioxide 〉=36.0%, silicon-dioxide≤0.0020%, titanium dioxide≤0.0005%, ferric oxide≤0.0005%, sodium oxide≤0.0010%, potassium oxide≤0.0005%, calcium oxide≤0.0005%, vitriol is (with SO
4 -2Meter)≤0.0005%.
2 one kinds of basic zirconium chloride crystallization apparatus of embodiment
This basic zirconium chloride crystallization apparatus, by the mixing component that comprises electric motor 1 and support thereof, reducing transmission structure 2, stir shaft 3 and stirring rake 4, and crystallization cavity 7 compositions that are provided with solution inlet 5 to be crystallized and generation crystal outlet 6.
It is the carbon steel manufacturing of Q235A that stirring rake 4 adopts the trade mark, and blade is an anchor formula blade, stirs, and stability is good.Reducing transmission structure 2 is rack pinion transmission groups, adds aluminum_alloy cover, and is aesthetic in appearance, and swing is stable, the safety performance height.Control stirring rake 4 velocities of rotation are 20～30 rev/mins.Electric motor 1 is 7.5 kilowatts.
The liner of the coating of stirring rake 4, crystallization cavity 7, and the liner of coupled pipeline, valve, matching used fluid reservoir all adopt the heatproof polypropylene high molecular material of 6 millimeters of thickness to make.
Claims (6)
1, the crystallization processes among a kind of basic zirconium chloride preparation method, it is characterized in that alkali fusion is arranged successively, washing, a pickling, acidifying, silica removal, concentrate, forced crystallization and white picking operation,
11 above-mentioned alkali fusion procedures are according to weight ratio 1: 1.05～1.40, with zircon sand and sodium hydroxide, to carry out alkali fusion in the alkali fusion stove that the input temperature is 750～1050 ℃, generation sodium zirconate and water glass;
12 above-mentioned washing steps are, according to volume ratio 1: 3～5, resultant and water with alkali fusion procedure stir at normal temperatures, separating solid substances and water lotion, and repetitive operation 3～5 times makes sodium zirconate separate with water glass;
13 above-mentioned pickling process are, according to volume ratio 1: 3～5, are 1～3 normal dilute hydrochloric acid with sodium zirconate and acidity, stir at normal temperatures, and separating solid substances and pickle solution, repetitive operation 3～5 times makes the zirconium in the sodium zirconate separate with sodium;
14 above-mentioned acidizing process are, the sodium zirconate that separates sodium is inserted in the acidification vessel, the control amount drops into the hydrochloric acid and the water of high density 27～30%, heated and boiled 10～30 minutes, make the sodium zirconate dissolving, generating acidity is 3～5 zirconium oxychloride solutions that equivalent, concentration are zirconium dioxide content 60～120 grams per liters;
15 above-mentioned silica removal operations are that according to weight ratio 1: 0.01～1.00 ‰, the zirconium oxychloride solution with the flocculation agent input generates left standstill 20～40 hours at normal temperatures, and the silicon in the solution is separated with basic zirconium chloride;
16 above-mentioned enrichment process are, the zirconium oxychloride solution of removing silicon is inserted in the concentration response still, feed steam in the heating jacket of reactor, it is 4.0～6.5 equivalents that the zirconium oxychloride solution heating is concentrated into acidity, and concentration is zirconium dioxide content 160～240 grams per liters;
17 above-mentioned forced crystallization operations are, spissated zirconium oxychloride solution is inserted in the special-purpose crystallization apparatus, control stirring rake velocity of rotation is 20～30 rev/mins, stirs 10～20 hours, sends into water coolant and cooling air with zirconium oxychloride solution, by 109～112 ℃ of beginnings of temperature forced cooling, when temperature drops to 70～80 ℃, begin to generate the basic zirconium chloride crystal, when temperature continues to drop to 30 ℃, substantially finish crystallisation process, generate saccharoidal pin type basic zirconium chloride crystal and mother liquor;
18 above-mentioned white picking operations are, pin type basic zirconium chloride crystal is soaked in 4.5～6.5 normal hydrochloric acid at normal temperatures, and soak time is 8～24 hours, insert again in the whizzer with 4.5～6.5 normal hydrochloric acid drip washing, and centrifugation.
2, the crystallization processes among the basic zirconium chloride preparation method as claimed in claim 1 is characterized in that the sodium hydroxide surrogate in the above-mentioned alkali fusion procedure, can be yellow soda ash, also can be lime carbonate, adopts the subsequent handling of surrogate, do corresponding adjustment.
3, the crystallization processes among the basic zirconium chloride preparation method as claimed in claim 1 is characterized in that the flocculation agent in the above-mentioned silica removal operation, can be polyacrylamide, also can be gelatin.
4, a kind of basic zirconium chloride crystallization apparatus by the mixing component that comprises electric motor and support thereof, reducing transmission structure, stir shaft and stirring rake, and is provided with solution inlet to be crystallized and generates the crystallization cavity composition that crystal exports, and it is characterized in that:
41 crystallization cavity also are provided with the water cooling chuck and the water coolant that is communicated with it is gone into, exported, and cooling air is gone into, exported;
The blade of 42 stirring rakes is anchor formula blades;
43 reducing transmission structures are rack pinion transmission groups, and control stirring rake velocity of rotation is 20～30 rev/mins;
The coating of 44 stirring rakes, the liner of crystallization cavity all adopt the heatproof high molecule material to make.
5, basic zirconium chloride crystallization apparatus as claimed in claim 4 is characterized in that:
Above-mentioned heatproof high molecule material can be a polypropylene.
6, as claim 4 or 5 described basic zirconium chloride crystallization apparatus, it is characterized in that:
The thickness of above-mentioned heatproof high molecule material is 4～10 millimeters.
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|---|---|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343174C (en) * | 2005-05-25 | 2007-10-17 | 宜兴新兴锆业有限公司 | High-purity ultra-fine zirconia production process |
| CN101830506A (en) * | 2010-05-18 | 2010-09-15 | 潍坊天福化学科技有限公司 | Preparation method of high-purity nano zirconium dioxide |
| CN102350084A (en) * | 2011-09-07 | 2012-02-15 | 浙江双子机械制造有限公司 | Medical nanometer crystallizing tank and crystallization method thereof |
| CN102500251A (en) * | 2011-10-14 | 2012-06-20 | 瓮福（集团）有限责任公司 | High-purity chemical dissolver |
| CN103318957A (en) * | 2013-06-20 | 2013-09-25 | 淄博广通化工有限责任公司 | Special zirconium oxychloride for coated cadmium selenide red ceramic pigment and preparation method thereof |
| CN103950977A (en) * | 2014-05-15 | 2014-07-30 | 李树昌 | Method for extracting zirconium oxide from zirconium-containing solid solution substance |
| CN104003439A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for preparing zirconium oxychloride solution |
| CN105233523A (en) * | 2015-11-13 | 2016-01-13 | 衢州妙凯节能科技有限公司 | Air blowing dredging stirrer |
| CN110980805A (en) * | 2019-12-19 | 2020-04-10 | 山东鸿远新材料科技有限公司 | Production process of high-purity zirconium oxychloride solution |
| CN115448362A (en) * | 2022-08-29 | 2022-12-09 | 焦天棋 | Method for separating and preparing zirconium salt and preparing zirconium oxide solid from zirconium oxychloride mother liquor |
-
2003
- 2003-04-02 CN CN 03114137 patent/CN1237008C/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343174C (en) * | 2005-05-25 | 2007-10-17 | 宜兴新兴锆业有限公司 | High-purity ultra-fine zirconia production process |
| CN101830506A (en) * | 2010-05-18 | 2010-09-15 | 潍坊天福化学科技有限公司 | Preparation method of high-purity nano zirconium dioxide |
| CN102350084A (en) * | 2011-09-07 | 2012-02-15 | 浙江双子机械制造有限公司 | Medical nanometer crystallizing tank and crystallization method thereof |
| CN102500251A (en) * | 2011-10-14 | 2012-06-20 | 瓮福（集团）有限责任公司 | High-purity chemical dissolver |
| CN104003439A (en) * | 2013-02-26 | 2014-08-27 | 中国科学院过程工程研究所 | Method for preparing zirconium oxychloride solution |
| CN104003439B (en) * | 2013-02-26 | 2016-04-06 | 中国科学院过程工程研究所 | A kind of method preparing zirconyl chloride solution |
| CN103318957A (en) * | 2013-06-20 | 2013-09-25 | 淄博广通化工有限责任公司 | Special zirconium oxychloride for coated cadmium selenide red ceramic pigment and preparation method thereof |
| CN103318957B (en) * | 2013-06-20 | 2015-07-15 | 淄博广通化工有限责任公司 | Special zirconium oxychloride for coated cadmium selenide red ceramic pigment and preparation method thereof |
| CN103950977A (en) * | 2014-05-15 | 2014-07-30 | 李树昌 | Method for extracting zirconium oxide from zirconium-containing solid solution substance |
| CN103950977B (en) * | 2014-05-15 | 2015-10-21 | 李树昌 | Zirconic method is extracted from containing zirconium solid solution material |
| CN105233523A (en) * | 2015-11-13 | 2016-01-13 | 衢州妙凯节能科技有限公司 | Air blowing dredging stirrer |
| CN110980805A (en) * | 2019-12-19 | 2020-04-10 | 山东鸿远新材料科技有限公司 | Production process of high-purity zirconium oxychloride solution |
| CN115448362A (en) * | 2022-08-29 | 2022-12-09 | 焦天棋 | Method for separating and preparing zirconium salt and preparing zirconium oxide solid from zirconium oxychloride mother liquor |
| CN115448362B (en) * | 2022-08-29 | 2024-01-16 | 焦天棋 | Method for separating and preparing zirconium salt from zirconium oxychloride mother solution and preparing zirconium oxide solid |
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| Publication number | Publication date |
|---|---|
| CN1237008C (en) | 2006-01-18 |
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Denomination of invention: Crystallization technology in preparation of zirconium oxychloride and its crystalization equipment Effective date of registration: 20170627 Granted publication date: 20060118 Pledgee: China the Great Wall asset management Limited by Share Ltd. Guangdong branch Pledgor: GUANGDONG ORIENT ZIRCONIC IND SCI & TECH CO.,LTD. Registration number: 2017990000545 |
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