CN102757091B - Method for preparing high-concentration titanic liquid - Google Patents

Method for preparing high-concentration titanic liquid Download PDF

Info

Publication number
CN102757091B
CN102757091B CN201110109344.2A CN201110109344A CN102757091B CN 102757091 B CN102757091 B CN 102757091B CN 201110109344 A CN201110109344 A CN 201110109344A CN 102757091 B CN102757091 B CN 102757091B
Authority
CN
China
Prior art keywords
titanium
concentration
liquid
intermediate product
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201110109344.2A
Other languages
Chinese (zh)
Other versions
CN102757091A (en
Inventor
薛天艳
王伟菁
杨轩
王丽娜
初景龙
齐涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Process Engineering of CAS
Original Assignee
Institute of Process Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Process Engineering of CAS filed Critical Institute of Process Engineering of CAS
Priority to CN201110109344.2A priority Critical patent/CN102757091B/en
Publication of CN102757091A publication Critical patent/CN102757091A/en
Application granted granted Critical
Publication of CN102757091B publication Critical patent/CN102757091B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention belongs to the field of treating inorganic compounds, and particularly relates to a method for preparing high-concentration titanic liquid from a solid intermediate product in titanium dioxide clean preparation technology by an alkaline molten salt method at one step. The amorphous solid intermediate product in the titanium dioxide clean preparation process by the alkaline molten salt method is used as a raw material, low-concentration sulfuric acid is adopted, and the high-concentration clear titanic liquid (with the concentration ranging from 220g/L to 300g/L measured by TiO2) is prepared under the condition of low-temperature acid hydrolysis at one step. Compared with the traditional titanium dioxide preparation technology by a sulfuric acid method, the method has the advantages that steps such as vacuum concentration can be omitted, and the concentration of the prepared titanic liquid is higher than that of titanium liquid prepared after a vacuum concentration step in the traditional sulfuric acid method; and titanium dioxide preparation processes are simplified, equipment investment is reduced, energy consumption is lowered, and productivity and product quality are improved.

Description

A kind of preparation method of high density titanium liquid
Technical field
The invention belongs to mineral compound manufacture field, specially refer to a kind of method that solid intermediate product (titanium-containing compound) step in alkali molten-salt growth method titanium white clearer production technology is prepared high density titanium liquid.
Background technology
Titanium dioxide is commonly called as titanium dioxide, is a kind of important source material in chemical industry, nontoxic, be harmless to the health, and it is most important white pigment, accounts for 80% of whole white pigment usage quantitys, consumes 90% titanium resource in the world, is the third-largest inorganic chemical product.Industrial process comprises sulfuric acid process and chlorination process, and the manufacturing enterprise of China 95% adopts sulfuric acid process, and this technical process is long, pollution is heavy, reaction medium cannot economic circulation utilization.
In recent years, Chinese Academy Of Sciences Process Engineering Research Institute has invented and has utilized sodium hydroxide, potassium hydroxide fused salt to decompose the clearer production technology (ZL 200610114130.3, ZL200610114131.8) that titanium resource is prepared titanium dioxide, this technology has advantages of that mineral efficiently decompose, medium economic circulation utilizes, polycomponent comprehensive utilization, and more traditional sulfuric acid process has obvious environmental benefit.But, the preparation process of titanium liquid and the character of gained titanium liquid are not further disclosed in patent (ZL200610114130.3, ZL 200610114131.8), and titanium liquid preparation process and titanium fluidity matter are one of core processes of clearer production technology, are related to and whether can prepare the titanium dioxide with excellent pigment performance.
Summary of the invention
The object of the invention is problem complicated for titanium liquid preparation process in traditional sulfuric acid process, that energy consumption is high, medium cannot economic circulation, proposing a kind of unbodied solid intermediate product (titanium-containing compound) of take in alkali molten-salt growth method titanium white clearer production technology is raw material, adopt low-concentration sulfuric acid, in low temperature acidolysis, next step prepares the method for high density clarification titanium liquid.
The present invention is that to take the solid intermediate product (compound of titaniferous) relating in alkali molten-salt growth method titanium white clearer production technology be raw material, adopt low-concentration sulfuric acid, in low temperature acidolysis, next step makes high density titanium liquid, this titanium liquid can make the uniform metatitanic acid of size distribution through hydrolysis, and metatitanic acid is through calcining, the coated titanium dioxide that can produce pigment performance excellence.
In tradition sulfate process titanium dioxide production technique, the raw material of acidolysis is ilmenite, ilmenite concentrate or the titanium slag of crystalline state, use the mass concentration > 85% of sulfuric acid, 180~200 ℃ of acidolysis temperatures, making titanium concentration scope is that 130~150g/L is (with TiO 2meter), need vacuum concentration to 190~200g/L (with TiO 2meter) be hydrolyzed again.Compare with acidolysis process in sulfuric acid process, in order to adopt, the solid intermediate product of amorphous state is raw material to feature of the present invention, use sulfuric acid concentration is low, acidolysis temperature is low, and the titanium liquid making can reach 220g/L (with TiO without concentrated 2meter) more than.Because sulfuric acid working concentration is low, the mother liquor after hydrolysis is reusable edible through preliminary concentrating.
The present invention is that the solid intermediate product of take in alkali molten-salt growth method titanium white clearer production technology is raw material, through low-concentration sulfuric acid, makes thick titanium liquid under low temperature acidolysis, and thick titanium liquid obtains high density clarification titanium liquid through flocculation, sedimentation, filtration.Method of the present invention comprises the following steps:
(1) dilute sulphuric acid that is 45%~70% by the solid intermediate product (titanium-containing compound) in alkali molten-salt growth method titanium white clearer production technology with mass concentration mixes, in temperature, be that at 30~80 ℃, insulated and stirred is carried out acidolysis (preferably the time of acidolysis is 1~72 hour, further preferably the time of acidolysis is 3~72 hours), standing (preferably the standing time is 1~24 hour), supernatant liquor is the thick titanium liquid that contains suspended solid;
(2) in the thick titanium liquid obtaining to step (1), add the modified polyacrylamide (AMPAM) as flocculation agent, in temperature, be insulated and stirred at 60~70 ℃ (time of preferably stirring is 3~6 hours), through flocculation, sedimentation, filtration, can obtain concentration is that 220~300g/L is (with TiO 2meter) clarification titanium liquid.
The solid-liquid mass ratio of described solid intermediate product and described dilute sulphuric acid is 1: 1~1.5: 1.
The crystal formation of described solid intermediate product is amorphous state, and wet basis titanium content is 25%~40% (with TiO 2meter).
Described solid intermediate product is the solid intermediate product described in ZL 200610114130.3 and ZL 200610114131.8; It is that titanium slag is mixed with sodium hydroxide, the solid-state intermediate product obtaining after reaction (general reaction times be 0.2~5 hour) at 350 ℃~550 ℃ obtains after washing (the solid-liquid mass ratio of solid-state intermediate product and water be preferably 1: 3~1: 100), and wherein the mass ratio of sodium hydroxide and titanium slag is 0.8: 1~3: 1; Or
Titanium slag is mixed with potassium hydroxide, at 380 ℃~500 ℃, after reaction (general reaction times be 0.2~3 hour), obtain solid-state intermediate product and obtain after washing (the solid-liquid mass ratio of solid-state intermediate product and water be preferably 1: 3~1: 100), wherein the mass ratio of potassium hydroxide and titanium slag is 0.5: 1~2: 1.
In the described thick titanium liquid obtaining to step (1), add modified polyacrylamide, the volume of the modified polyacrylamide adding be thick titanium liquid long-pending 3%~10%, the mass concentration of modified polyacrylamide is 0.1%~1%.
In described titanium slag, the mass content of titanium dioxide is greater than 85%.
The main component of described clarification titanium liquid is sulfuric acid, titanium sulfate and titanyl sulfate; The effective acid concentration of described clarification titanium liquid is that 300~600g/L is (with H 2sO 4meter).
The more traditional sulfate process titanium dioxide production technology of the present invention, can save the steps such as vacuum concentration, and the titanium concentration of the titanium concentration obtaining after higher than vacuum concentration, simplified Producing Titanium Dioxide flow process, reduce equipment investment, reduced energy consumption, improved production capacity and quality product.
The present invention compares with traditional sulfuric acid process acidolysis process, and the present invention has following advantage: (1) acidolysis is low with sulfuric acid concentration, mother liquor after titanium hydrolysis through preliminary concentrated can economic circulation utilization, reduce acid consumption and spent acid quantity discharged; (2) acidolysis temperature is low, easy to operate, energy consumption is low, low for equipment requirements; (3) titanium concentration making is high, can increase substantially production capacity and product pigment performance.
Embodiment
Embodiment 1
Utilize the method in ZL 200610114130.3 and ZL 200610114131.8 to prepare solid intermediate product (titanium-containing compound); The mass content of titanium dioxide being greater than to 85% titanium slag mixes with sodium hydroxide, at 350 ℃~550 ℃, react 0.2~5 hour, wherein the mass ratio of sodium hydroxide and titanium slag is 0.8: 1~3: 1, the solid-state intermediate product obtaining and water be take solid-liquid mass ratio and were washed as 1: 3~1: 100, make the solid intermediate product after washing; Or
The mass content of titanium dioxide being greater than to 85% titanium slag mixes with potassium hydroxide, at 380 ℃~500 ℃, react 0.2~3 hour, wherein the mass ratio of potassium hydroxide and titanium slag is 0.5: 1~2: 1, the solid-state intermediate product obtaining and water be take solid-liquid mass ratio and were washed as 1: 3~1: 100, make the solid intermediate product after washing.
(wet basis titanium content is 32% to the solid intermediate product that to get crystal formation that 180g aforesaid method prepares be amorphous state, with TiO 2meter) sulphuric acid soln that is 60% with 100mL mass concentration mixes, the solid-liquid mass ratio of solid intermediate product and dilute sulphuric acid is 1.2: 1, in temperature, is insulated and stirred 8 hours at 50 ℃, standing 4 hours, the supernatant liquor that taking-up contains trace suspension thing, obtains the thick titanium liquid of 200mL; To adding 10mL mass concentration in the thick titanium liquid of the 200mL obtaining, being 0.1% AMPAM flocculation agent, is insulated and stirred 4 hours at 60 ℃ in temperature, and through flocculation, sedimentation, filtration, the main component of analyzing gained clarification titanium liquid is sulfuric acid, titanium sulfate and titanyl sulfate; The effective acid concentration of described clarification titanium liquid is that 400~420g/L is (with H 2sO 4meter), the concentration of titanium dioxide is that 235~240g/L is (with TiO 2meter).
Embodiment 2
With reference to embodiment 1, prepare solid intermediate product (titanium-containing compound); (wet basis titanium content is 40% to the solid intermediate product that to get crystal formation that 200g prepares be amorphous state, with TiO 2meter) be that 70% sulphuric acid soln mixes with 100mL mass concentration, the solid-liquid mass ratio of solid intermediate product and dilute sulphuric acid is 1.2: 1, in temperature, is insulated and stirred 4 hours at 30 ℃, standing 12 hours, the supernatant liquor that taking-up contains trace suspension thing, obtains the thick titanium liquid of 200mL; To adding 6mL mass concentration in the thick titanium liquid obtaining, being 1% AMPAM flocculation agent, is insulated and stirred 6 hours at 65 ℃ in temperature, and through flocculation, sedimentation, filtration, the main component of analyzing gained clarification titanium liquid is sulfuric acid, titanium sulfate and titanyl sulfate; The effective acid concentration of described clarification titanium liquid is that 580~600g/L is (with H 2sO 4meter), the concentration of titanium dioxide is that 290~300g/L is (with TiO 2meter).
Embodiment 3
With reference to embodiment 1, prepare solid intermediate product (titanium-containing compound); (wet basis titanium content is 25% to the solid intermediate product that to get crystal formation that 160g prepares be amorphous state, with TiO 2meter) be that 50% sulphuric acid soln mixes with 100mL mass concentration, the solid-liquid mass ratio of solid intermediate product and dilute sulphuric acid is 1.1: 1, in temperature, is insulated and stirred 72 hours at 60 ℃, standing 1 hour, the supernatant liquor that taking-up contains trace suspension thing, obtains the thick titanium liquid of 150mL; To adding 15mL mass concentration in the thick titanium liquid obtaining, being 0.5% AMPAM flocculation agent, is insulated and stirred 3 hours at 70 ℃ in temperature, and through flocculation, sedimentation, filtration, the main component of analyzing gained clarification titanium liquid is sulfuric acid, titanium sulfate and titanyl sulfate; The effective acid concentration of described clarification titanium liquid is that 300~320g/L is (with H 2sO 4meter), the concentration of titanium dioxide is that 220~225g/L is (with TiO 2meter).
Embodiment 4
With reference to embodiment 1, prepare solid intermediate product (titanium-containing compound); (wet basis titanium content is 38% to the solid intermediate product that to get crystal formation that 160g prepares be amorphous state, with TiO 2meter) be that 70% sulphuric acid soln mixes with 100mL mass concentration, the solid-liquid mass ratio of solid intermediate product and dilute sulphuric acid is 1.0: 1, in temperature, is insulated and stirred 24 hours at 40 ℃, standing 3 hours, the supernatant liquor that taking-up contains trace suspension thing, obtains the thick titanium liquid of 160mL; To adding 8mL mass concentration in the thick titanium liquid obtaining, being 1% AMPAM flocculation agent, is insulated and stirred 3 hours at 65 ℃ in temperature, and through flocculation, sedimentation, filtration, the main component of analyzing gained clarification titanium liquid is sulfuric acid, titanium sulfate and titanyl sulfate; The effective acid concentration of described clarification titanium liquid is that 520~540g/L is (with H 2sO 4meter), the concentration of titanium dioxide is that 240~245g/L is (with TiO 2meter).
Embodiment 5
With reference to embodiment 1, prepare solid intermediate product (titanium-containing compound); (wet basis titanium content is 30% to the solid intermediate product that to get crystal formation that 200g prepares be amorphous state, with TiO 2meter) be that 45% sulphuric acid soln mixes with 100mL mass concentration, the solid-liquid mass ratio of solid intermediate product and dilute sulphuric acid is 1.5: 1, in temperature, is insulated and stirred 6 hours at 40 ℃, standing 24 hours, the supernatant liquor that taking-up contains trace suspension thing, obtains the thick titanium liquid of 200mL; To adding 10mL mass concentration in the thick titanium liquid obtaining, being 0.8% AMPAM flocculation agent, is insulated and stirred 6 hours at 65 ℃ in temperature, and through flocculation, sedimentation, filtration, the main component of analyzing gained clarification titanium liquid is sulfuric acid, titanium sulfate and titanyl sulfate; The effective acid concentration of described clarification titanium liquid is that 320~340g/L is (with H 2sO 4meter), the concentration of titanium dioxide is that 235~240g/L is (with TiO 2meter).

Claims (7)

1. a preparation method for high density titanium liquid, is characterized in that: described method comprises the following steps:
(1) dilute sulphuric acid that is 45%~70% by the solid intermediate product in alkali molten-salt growth method titanium white clearer production technology with mass concentration mixes, and in temperature, is that at 30~80 ℃, insulated and stirred is carried out acidolysis, standing, and supernatant liquor is the thick titanium liquid that contains suspended solid; Wherein, the solid-liquid mass ratio of described solid intermediate product and described dilute sulphuric acid is 1:1~1.5:1;
(2) in the thick titanium liquid obtaining to step (1), adding modified polyacrylamide, is insulated and stirred at 60~70 ℃ in temperature, and through flocculation, sedimentation, filtration, obtaining concentration is that 220~300g/L is (with TiO 2meter) clarification titanium liquid;
Described solid intermediate product is that titanium slag is mixed with sodium hydroxide, and the solid-state intermediate product obtaining after reaction at 350 ℃~550 ℃ obtains after washing, and wherein the mass ratio of sodium hydroxide and titanium slag is 0.8:1~3:1; Or
Titanium slag is mixed with potassium hydroxide, obtain solid-state intermediate product and obtain after washing at 380 ℃~500 ℃ after reaction, wherein the mass ratio of potassium hydroxide and titanium slag is 0.5:1~2:1;
The crystal formation of described solid intermediate product is amorphous state, and wet basis titanium content is 25%~40% (with TiO 2meter);
In described titanium slag, the mass content of titanium dioxide is greater than 85%.
2. method according to claim 1, is characterized in that: the time of described acidolysis is 1~72 hour.
3. method according to claim 2, is characterized in that: the time of described acidolysis is 3~72 hours.
4. method according to claim 1, is characterized in that: the described standing time is 1~24 hour.
5. method according to claim 1, is characterized in that: the time of the insulated and stirred that step (2) is described is 3~6 hours.
6. method according to claim 1, it is characterized in that: in the described thick titanium liquid obtaining to step (1), add modified polyacrylamide, the volume of the modified polyacrylamide adding be thick titanium liquid long-pending 3%~10%, the mass concentration of modified polyacrylamide is 0.1%~1%.
7. method according to claim 1, is characterized in that: the main component of described clarification titanium liquid is sulfuric acid, titanium sulfate and titanyl sulfate; The effective acid concentration of described clarification titanium liquid is that 300~600g/L is (with H 2sO 4meter).
CN201110109344.2A 2011-04-28 2011-04-28 Method for preparing high-concentration titanic liquid Active CN102757091B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110109344.2A CN102757091B (en) 2011-04-28 2011-04-28 Method for preparing high-concentration titanic liquid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110109344.2A CN102757091B (en) 2011-04-28 2011-04-28 Method for preparing high-concentration titanic liquid

Publications (2)

Publication Number Publication Date
CN102757091A CN102757091A (en) 2012-10-31
CN102757091B true CN102757091B (en) 2014-07-30

Family

ID=47051781

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110109344.2A Active CN102757091B (en) 2011-04-28 2011-04-28 Method for preparing high-concentration titanic liquid

Country Status (1)

Country Link
CN (1) CN102757091B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103553126B (en) * 2013-11-07 2016-05-04 天津致远投资集团有限公司 A kind of method of preparing titanium dioxide with low-concentration alkali liquor
CN109354060A (en) * 2018-08-20 2019-02-19 江苏钛谷科技有限公司 A kind of technique of clean manufacturing titanium dioxide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001294424A (en) * 2000-04-07 2001-10-23 Nippon Steel Weld Prod & Eng Co Ltd Method for manufacturing sodium titanate
CN101172648A (en) * 2006-10-30 2008-05-07 中国科学院过程工程研究所 Method for clean production of titanium dioxide by using sodium hydroxide
CN101172649A (en) * 2006-10-30 2008-05-07 中国科学院过程工程研究所 Method for clean production of titanium dioxide by using potassium hydroxide
CN101812595A (en) * 2010-05-06 2010-08-25 北京矿冶研究总院 Method for producing synthetic rutile by using titania slag

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001294424A (en) * 2000-04-07 2001-10-23 Nippon Steel Weld Prod & Eng Co Ltd Method for manufacturing sodium titanate
CN101172648A (en) * 2006-10-30 2008-05-07 中国科学院过程工程研究所 Method for clean production of titanium dioxide by using sodium hydroxide
CN101172649A (en) * 2006-10-30 2008-05-07 中国科学院过程工程研究所 Method for clean production of titanium dioxide by using potassium hydroxide
CN101812595A (en) * 2010-05-06 2010-08-25 北京矿冶研究总院 Method for producing synthetic rutile by using titania slag

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
《氢氧化钠熔盐分解高钛渣制备二氧化钛清洁新工艺的研究》;薛天艳;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20090831(第09期);第I、34、38-39、84页 *
薛天艳.《氢氧化钠熔盐分解高钛渣制备二氧化钛清洁新工艺的研究》.《中国博士学位论文全文数据库 工程科技Ⅰ辑》.2009,(第09期),第I、34、38-39、84页.
陈朝华.《钛白粉生产技术问答》.《钛白粉生产技术问答》.化学工业出版社,1998,(第1版),第67-70页. *
陈朝华等.《钛白粉生产及应用技术》.《钛白粉生产及应用技术》.化学工业出版社材料科学与工程出版中心,2006,(第1版),第234页. *

Also Published As

Publication number Publication date
CN102757091A (en) 2012-10-31

Similar Documents

Publication Publication Date Title
CN102616836B (en) Preparation method of trivalent titanium solution
CN102390865B (en) Method for preparing high-activity double-effect seed crystals from metatitanic acid
CN104817105B (en) Preparation method for treating titanium white by high zinc salt
CN102828037B (en) Method of preparing low-silicon low-phosphorus potassium metavanadate solution from vanadium slag
CN106082319A (en) A kind of preparation method of sulfuric acid method titanium pigment production mixed crystal type double-effect seed crystal
CN101671051B (en) Titanium dioxide hydrolysis particle whitening agent and preparation method of titanium dioxide hydrolysis crystal seed
CN102303904B (en) Hydrolysis method for preparing high-brightness rutile titanium white from low-concentration titaniferous solution
CN106745234A (en) The preparation method of rutile type titanium white
CN103145193B (en) A kind of by-product of white titanium pigment prepares the method for iron oxide yellow
CN102153136B (en) Preparation method of hydrated titanium dioxide double-effect seed crystal
CN107963656A (en) The method that titanium slag preparation pigmentary titanium dioxide is decomposed using mixed acid
CN102757091B (en) Method for preparing high-concentration titanic liquid
CN102701240A (en) Method for preparing silicon-steel-grade magnesium oxide from magnesium sulfate waste liquor
CN103482695A (en) Method for low-temperature production of titanium dioxide by mixed alkali of sodium hydroxide and potassium hydroxide
CN103145194B (en) A kind of method utilizing by-product of white titanium pigment to prepare iron oxide yellow
CN101190800A (en) Method for preparing rutile-type titanium dioxide by hydrothermal method
CN102765752A (en) Method for producing rutile type titanium dioxide through metatitanic acid direct diolame
CN103950976A (en) Method for preparing titanium dioxide by utilizing mixed alkali of sodium hydroxide and sodium nitrate
CN102432066B (en) Method for preparing titanium tetrachloride hydrolyzed crystal seed
CN103274460B (en) Method for preparing rutile phase titanium dioxide sub-microsphere through selective dispergation
CN101804992A (en) Method for preparing superfine aluminium silicate by bentonite
CN103787362B (en) A kind of technique utilizing import gibbsite-type bauxite to prepare 4A molecular sieve
CN104098135A (en) Recycling method of alkali-soluble filtrate
CN108906014A (en) A kind of high temperature resistant visible-light-responsive photocatalyst and preparation method thereof
CN105905941A (en) Low concentration hydrolysis method in sulfuric acid method titanium dioxide technology

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant