CN111422905A - Preparation method of zirconium sulfate - Google Patents
Preparation method of zirconium sulfate Download PDFInfo
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- CN111422905A CN111422905A CN202010256251.1A CN202010256251A CN111422905A CN 111422905 A CN111422905 A CN 111422905A CN 202010256251 A CN202010256251 A CN 202010256251A CN 111422905 A CN111422905 A CN 111422905A
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- zirconium sulfate
- zircon sand
- filtrate
- sulfuric acid
- acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/06—Sulfates
Abstract
The invention discloses a preparation method of zirconium sulfate, which comprises the following steps: and (3) reacting the crushed zircon sand with sulfuric acid for 3-5 hours under the condition of pressurization and heating, sequentially adding water for washing and filtering after the reaction is finished, collecting filtrate, removing impurities in the filtrate, and crystallizing the obtained zirconium sulfate solution to obtain zirconium sulfate. The invention adopts the method of directly reacting zircon sand with sulfuric acid under the conditions of heating and pressurizing to prepare zirconium sulfate, does not adopt alkali fusion, avoids using sodium hydroxide or sodium carbonate, saves the step of sodium removal, and can obtain high-purity zirconium sulfate only by crystallizing once.
Description
Technical Field
The invention belongs to the field of zirconium sulfate preparation, and particularly relates to a zirconium sulfate preparation method.
Background
Zirconium sulfate is an intermediate product for preparing other zirconium compounds, can also be sold as a finished product, and is used in the industries of rubber, papermaking, tanning and the like. There are many methods for producing zirconium sulfate, and the method for producing zirconium sulfate from zirconite includes: (1) zircon → alkali fusion → water washing → sulfuric acid leaching → ammonia precipitation → washing for sodium removal → sulfuric acid dissolution → evaporative crystallization → recrystallization → zirconium sulfate product; (2) zircon → alkali fusion → water washing → hydrochloric acid leaching → hydrolysis → sulfuric acid dissolution → crystallization → zirconium sulfate product. There are the following disadvantages from the two methods described above:
(1) in the first method and the second method, alkali fusion is used, and the alkali fusion raw material is generally sodium hydroxide or sodium carbonate, so that the subsequent sodium removal step is added, and Na is formed2[ZrO(SO4)2]·3H2The compound salt of O is not easy to clean sodium; (2) the first method and the second method both have an alkali fusion step, so an acid liquor leaching step needs to be added, the first method adopts sulfuric acid leaching, the amount of sulfuric acid needs to be accurately controlled, the sulfuric acid is insufficient, and Na in the transfer molding material is contained2ZrSiO5The leaching is difficult, the leaching rate is low, the silicic acid is not easy to agglomerate, the filtering is difficult, the sulfuric acid is excessive, the acidity of the leaching solution is too high, the evaporation is difficult, silica gel is easy to form in the evaporation process, and the filtering is difficult; in the second method, hydrochloric acid is adopted for leaching, so that the hydrochloric acid easily causes serious corrosion to production equipment; (3) the first method needs recrystallization to obtain high-purity zirconium sulfate, and the second method adopts low-acid leaching and high-acid dissolution, so that the product yield is low.
Disclosure of Invention
In order to solve the problems, the invention provides a zirconium sulfate preparation method, which directly reacts zircon sand and sulfuric acid under heating and pressurizing conditions, so that alkali fusion is avoided, production steps are saved, and production efficiency is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of zirconium sulfate comprises the following steps: and (3) reacting the crushed zircon sand with sulfuric acid for 3-5 hours under the condition of pressurization and heating, sequentially adding water for washing and filtering after the reaction is finished, collecting filtrate, removing impurities in the filtrate, and crystallizing the obtained zirconium sulfate solution to obtain zirconium sulfate.
Further, the reaction temperature is 200-230 ℃.
Further, the reaction pressure was 0.5 MPa.
Further, the zircon sand is crushed into fine powder with the grain diameter of less than 325 meshes.
Furthermore, the mass ratio of the zircon sand to the sulfuric acid is 1: 5.5-7.
Further, the concentration of sulfuric acid is 65-70%.
Furthermore, the water adding amount for washing by adding water is 5-20 times of the mass of the zircon sand.
Further, the method for removing the impurities in the filtrate is that the complexing agent is added into the mixed solution to be stirred and reacted, the reaction temperature is 60-80 ℃, and the reaction time is 2-3 h.
Further, the complexing agent comprises oxalic acid, pyrophosphoric acid or hydrochloric acid.
Further, the method for removing the impurities in the filtrate is to filter or adsorb the iron element in the filtrate through a filter membrane or an adsorbent to obtain the zirconium sulfate solution, wherein the filter membrane is an acid liquid homogeneous phase filter membrane, and the adsorbent is heavy metal ion exchange resin.
The principle of the invention is as follows: the zircon sand directly reacts with sulfuric acid under heating and pressurizing, after a product is washed and leached, silicic acid and partial titanium dioxide solid impurities are filtered, zirconium sulfate, ferric sulfate and trace titanium are contained in a filtrate, ferric sulfate in the filtrate is removed, a higher zirconium sulfate solution is obtained and is subjected to crystallization treatment, zirconium sulfate is crystallized and separated out, and trace titanium impurities are left in a mother solution, so that high-purity zirconium sulfate crystals are obtained, and recrystallization is avoided.
Compared with the prior art, the invention has the beneficial effects that:
(1) the zirconium sulfate is prepared by directly reacting zircon sand with sulfuric acid under the conditions of heating and pressurizing without adopting alkali fusion, so that sodium hydroxide or sodium carbonate is avoided, the step of removing sodium is saved, and the high-purity zirconium sulfate can be obtained only by crystallizing once; (2) when the zirconium sulfate is prepared, under the condition of heating and pressurizing, reactants are only zircon sand and sulfuric acid, and other auxiliary agents are not added, so that new impurities are prevented from being substituted or harmful waste gas is prevented from being generated, the harmful waste gas is prevented from being generated, and the environment protection is facilitated; (3) the method has short process route, and is beneficial to improving the production efficiency; (4) one method for removing impurities in the filtrate is to adopt a complexing agent to complex ferric ions into a complex compound which is easy to dissolve in water, so that zirconium sulfate is crystallized and separated out during crystallization, and the iron complex compound and trace titanium are left in the mother liquor to be removed; (5) in another method for removing the impurities in the filtrate, a proper filtering membrane or an adsorbent is selected, the impurities are filtered or adsorbed to obtain a high-purity zirconium sulfate solution, and then the high-purity zirconium sulfate solution is crystallized to obtain a high-purity zirconium sulfate crystal product.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. All other embodiments that can be obtained by a person skilled in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.
Example 1
Crushing zircon sand into zircon sand fine powder with the particle size smaller than 325 meshes, and reacting the zircon sand fine powder with sulfuric acid for 5 hours under the conditions of 0.5MPa and 200 ℃, wherein the mass ratio of the zircon sand to the sulfuric acid is 1:5.5, and the concentration of the sulfuric acid is 70%; after the reaction is finished, cooling to below 100 ℃, adding water which is 5 times of the mass of the zircon sand, stirring and washing, then filtering and collecting filtrate, adding oxalic acid into the filtrate for complexing, wherein the mass of the oxalic acid is 3.5 times of that of the ferric oxide, the reaction temperature is 60 ℃, reacting for 2 hours, and crystallizing the obtained solution to obtain zirconium sulfate.
Example 2
Crushing zircon sand into zircon sand fine powder with the particle size smaller than 325 meshes, and reacting the zircon sand fine powder with sulfuric acid for 4 hours under the conditions of 0.5MPa and 210 ℃, wherein the mass ratio of the zircon sand to the sulfuric acid is 1:5.6, and the concentration of the sulfuric acid is 68%; after the reaction is finished, cooling to below 100 ℃, adding water which is 10 times of the mass of the zircon sand, stirring and washing, then filtering and collecting filtrate, adding pyrophosphoric acid into the filtrate for complexing, wherein the mass of the pyrophosphoric acid is 2.6 times of that of ferric oxide, the reaction temperature is 65 ℃, reacting for 2.5 hours, and crystallizing the obtained solution to obtain zirconium sulfate.
Example 3
Crushing zircon sand into zircon sand fine powder with the particle size smaller than 325 meshes, and reacting the zircon sand fine powder with sulfuric acid for 3 hours under the conditions of 0.5MPa and 220 ℃, wherein the mass ratio of the zircon sand to the sulfuric acid is 1:5.7, and the concentration of the sulfuric acid is 65%; after the reaction is finished, cooling to below 100 ℃, adding water which is 15 times of the mass of the zircon sand, stirring and washing, then filtering and collecting filtrate, adding hydrochloric acid into the filtrate for complexing, wherein the mass of the hydrochloric acid is 1.8 times of that of ferric oxide, the reaction temperature is 70 ℃, reacting for 2.5 hours, and crystallizing the obtained solution to obtain zirconium sulfate.
Example 4
Crushing zircon sand into zircon sand fine powder with the particle size smaller than 325 meshes, and reacting the zircon sand fine powder with sulfuric acid for 3 hours under the conditions of 0.5MPa and 230 ℃, wherein the mass ratio of the zircon sand to the sulfuric acid is 1:6, and the concentration of the sulfuric acid is 70%; after the reaction is finished, cooling to below 100 ℃, adding water which is 20 times of the mass of the zircon sand, stirring and washing, then filtering and collecting filtrate, adding pyrophosphoric acid into the filtrate for complexing, wherein the mass of the pyrophosphoric acid is 2.6 times of that of ferric oxide, the reaction temperature is 80 ℃, reacting for 3 hours, and crystallizing the obtained solution to obtain zirconium sulfate.
Example 5
Crushing zircon sand into zircon sand fine powder with the particle size smaller than 325 meshes, and reacting the zircon sand fine powder with sulfuric acid for 3 hours under the conditions of 0.5MPa and 230 ℃, wherein the mass ratio of the zircon sand to the sulfuric acid is 1:6, and the concentration of the sulfuric acid is 70%; after the reaction is finished, cooling to below 100 ℃, adding water which is 20 times of the mass of the zircon sand, stirring and washing, then filtering and collecting filtrate, filtering the obtained filtrate by adopting a peracid liquid homogeneous phase filter membrane to obtain a filtered high-purity zirconium sulfate solution, and crystallizing the obtained solution to obtain zirconium sulfate.
Example 6
Crushing zircon sand into zircon sand fine powder with the particle size smaller than 325 meshes, and reacting the zircon sand fine powder with sulfuric acid for 3 hours under the conditions of 0.5MPa and 230 ℃, wherein the mass ratio of the zircon sand to the sulfuric acid is 1:6, and the concentration of the sulfuric acid is 70%; after the reaction is finished, cooling to below 100 ℃, adding water which is 20 times of the mass of the zircon sand, stirring and washing, then filtering and collecting filtrate, adsorbing impurities in the filtrate by adopting heavy metal ion exchange resin to obtain a high-purity zirconium sulfate solution, and crystallizing the high-purity zirconium sulfate solution to obtain zirconium sulfate.
A zircon starting material having an iron trioxide content of 0.1%, a titanium dioxide content of 0.39% and a silicon dioxide content of 33.04% was purchased, and zirconium sulfate was produced by the methods of examples 1 to 6. And (3) carrying out impurity detection on the obtained zirconium sulfate product according to a method specified in the industry standard HG/T3786-2005 industrial zirconium sulfate.
Table 1 units of test results: is based on
| Experimental example 1 | Experimental example 2 | Experimental example 3 | Experimental example 4 | Experimental example 5 | Experimental example 6 | |
| Fe2O3Mass fraction | 0.007 | 0.006 | 0.006 | 0.004 | 0.005 | 0.005 |
| SiO2Mass fraction | 0.016 | 0.013 | 0.012 | 0.007 | 0.012 | 0.014 |
| TiO2Mass fraction | 0.0016 | 0.0013 | 0.0013 | 0.0009 | 0.0012 | 0.0017 |
Claims (9)
1. The preparation method of zirconium sulfate is characterized by comprising the following steps: and (3) reacting the crushed zircon sand with sulfuric acid for 3-5 hours under the condition of pressurization and heating, sequentially adding water for washing and filtering after the reaction is finished, collecting filtrate, removing impurities in the filtrate, and crystallizing the obtained zirconium sulfate solution to obtain zirconium sulfate.
2. The method as claimed in claim 1, wherein the reaction temperature is 200-230 ℃.
3. The method according to claim 1, wherein the reaction pressure is 0.5 MPa.
4. The method of claim 1, wherein the zircon sand is pulverized into fine powder with a particle size of less than 325 meshes.
5. The method for preparing zirconium sulfate according to claim 1, wherein the concentration of sulfuric acid is 65-70%, and the mass ratio of zircon sand to sulfuric acid is 1: 5.5-6.
6. The method of claim 1, wherein the amount of water added for washing is 5-20 times the mass of the zircon sand.
7. The method according to any one of claims 1 to 6, wherein the impurities in the filtrate are removed by adding a complexing agent to the mixed solution and stirring the mixed solution for reaction at a temperature of 60 to 80 ℃ for 2 to 3 hours.
8. The method according to claim 7, wherein the complexing agent comprises oxalic acid, pyrophosphoric acid, hydrochloric acid.
9. The method according to any one of claims 1 to 6, wherein the impurities in the filtrate are removed by filtering or adsorbing the iron element in the filtrate with a filtering membrane or an adsorbent, the filtering membrane is an acid solution homogeneous filtering membrane, and the adsorbent is a heavy metal ion exchange resin, to obtain the zirconium sulfate solution.
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| CN202010256251.1A CN111422905A (en) | 2020-04-02 | 2020-04-02 | Preparation method of zirconium sulfate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262806A (en) * | 2021-12-13 | 2022-04-01 | 先导薄膜材料（广东）有限公司 | Method for recycling scandium and zirconium from waste solid oxide fuel cell |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3168374A (en) * | 1960-09-03 | 1965-02-02 | Degussa | Production of zirconium compounds from alkali metal-zirconium silicates |
| US4746497A (en) * | 1985-02-01 | 1988-05-24 | Commonwealth Scientific And Industrial Research Organization | Process for the production of high purity zirconia |
| WO2001042520A1 (en) * | 1999-12-13 | 2001-06-14 | Pacmin Investments Limited | Method of high-temperature digesting titanium containing material with sulfuric acid |
| US20070292332A1 (en) * | 2004-05-27 | 2007-12-20 | Ettienne Snyders | Upgrading of Zircon |
| CN101292052A (en) * | 2005-10-18 | 2008-10-22 | 美礼联无机化工公司 | Titaniferous ore beneficiation |
| CN103253700A (en) * | 2012-02-15 | 2013-08-21 | 淄博市周村磊宝耐火材料有限公司 | Method for purification of zircon sand to prepare high purity zirconia |
| CN107531508A (en) * | 2015-02-09 | 2018-01-02 | 艾绿卡资源有限公司 | The method for improving zircon grade and optical quality |
-
2020
- 2020-04-02 CN CN202010256251.1A patent/CN111422905A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3168374A (en) * | 1960-09-03 | 1965-02-02 | Degussa | Production of zirconium compounds from alkali metal-zirconium silicates |
| US4746497A (en) * | 1985-02-01 | 1988-05-24 | Commonwealth Scientific And Industrial Research Organization | Process for the production of high purity zirconia |
| WO2001042520A1 (en) * | 1999-12-13 | 2001-06-14 | Pacmin Investments Limited | Method of high-temperature digesting titanium containing material with sulfuric acid |
| US20070292332A1 (en) * | 2004-05-27 | 2007-12-20 | Ettienne Snyders | Upgrading of Zircon |
| CN101292052A (en) * | 2005-10-18 | 2008-10-22 | 美礼联无机化工公司 | Titaniferous ore beneficiation |
| CN103253700A (en) * | 2012-02-15 | 2013-08-21 | 淄博市周村磊宝耐火材料有限公司 | Method for purification of zircon sand to prepare high purity zirconia |
| CN107531508A (en) * | 2015-02-09 | 2018-01-02 | 艾绿卡资源有限公司 | The method for improving zircon grade and optical quality |
Non-Patent Citations (1)
| Title |
|---|
| 陈静等: "由锆英石制备硫酸锆的工艺研究", 《广东化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262806A (en) * | 2021-12-13 | 2022-04-01 | 先导薄膜材料（广东）有限公司 | Method for recycling scandium and zirconium from waste solid oxide fuel cell |
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