CN1062125A - The titanium dioxide method for making of using sulphate to partly replace titanium white - Google Patents

The titanium dioxide method for making of using sulphate to partly replace titanium white Download PDF

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CN1062125A
CN1062125A CN 90109773 CN90109773A CN1062125A CN 1062125 A CN1062125 A CN 1062125A CN 90109773 CN90109773 CN 90109773 CN 90109773 A CN90109773 A CN 90109773A CN 1062125 A CN1062125 A CN 1062125A
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hydrolysis
titanium
titanium dioxide
liquid
stirring reaction
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鲍学昭
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Abstract

The titanium dioxide method for making of using sulphate to partly replace titanium white is to belong to a kind of using sulphate to partly replace TiO 2Vitriol is produced the method for titanium dioxide.
The present invention is characterised in that and set up stirring reaction and mix operation before hydrolysis process, and the hydrolysis calcining process has been done some improvement, can improve the quality of products.Use the present invention can utilize vitriol and natural mineral partly to substitute TiO 2Produce titanium dioxide, cost reduces, and realizes ordinary production, and quality product can reach domestic standard laid down by the ministries or commissions of the Central Government one-level or secondary standard.

Description

The titanium dioxide method for making of using sulphate to partly replace titanium white
The present invention relates to a kind of titanium white production method of using sulphate to partly replace titanium dioxide, extensively be suitable for the titanium dioxide product of producing different purposes, be particularly useful for producing coating level titanium dioxide.
The cheap CaCO of the present invention 3, CaO, CaSO 4, BaSO 4And other compound that can form sulfate precipitation with sulfuric acid reaction participates in hydrolytic process finally with CaSO with the effect of titanium liquid 4Produce titanium dioxide and do not damage the pigment performance of titanium white Deng the form part replacement of titanium dioxide of vitriol.Reduced cost, simultaneously CaCO 3The adding of above-mentioned substances such as CaO has also promoted hydrolysis to carry out, and the final product quality is good and stablize, and the more important thing is and can carry out ordinary-pressure hydrolysis or letter when the equipment ordinary-pressure hydrolysis in original production titanium dioxide equipment, just can produce high-quality titanium dioxide product.
The main method of producing at present titanium dioxide has sulfuric acid process and chlorination process, and domestic most of Producing Titanium Dioxide producer all adopts the Production By Sulfuric Acid Process titanium white.Fig. 1 is that it has represented the main processes of present Production By Sulfuric Acid Process titanium white according to 36 pages of technological process synoptic diagram of going up after process flow sheet is simplified of document " sulfate process titanium dioxide production " (Chemical Industry Press Beijing in February nineteen eighty-two is version for the first time).Perovskite powder after pulverizing by acidolysis (1) acidolysis also makes titanium liquid (2) through operations such as reduction, sedimentation, crystallizations, add crystal seed through hydrolysis (3) and metatitanic acid or positive metatitanic acid are handled (5), calcining (6), are pulverized (7) and promptly get the titanium dioxide product through bleaching washing (4), salt successively again.
The required condition of hydrolysis in the above producing and manufacturing technique (3) technology is tighter, difficult the grasp, generally need pressurized hydrolysis, domestic production titanium white producer all uses this technology, but the titanium dioxide difficult quality reaches domestic standard laid down by the ministries or commissions of the Central Government one-level or secondary standard, and produce pure titanium dioxide and present worldwide titanium resource anxiety contradicts, production cost will be more and more higher.
The objective of the invention is to use CaCO 3, CaO or CaSO 4, BaSO 4Deng participating in hydrolytic process, improve hydrolysis rate and improve the tinting strength of titanium dioxide, and in the final product with CaSO 4Form in vitriol partly substitutes titanium white 0-40% and does not damage its pigment performance, if realize that with this technology normalizing production, quality product meet domestic standard laid down by the ministries or commissions of the Central Government first class product or secondary product removes TiO 2Every index request beyond the content.
The present invention is achieved in that in conjunction with the accompanying drawings and 2 is described as follows:
Fig. 2 is a using sulphate to partly replace Producing Titanium Dioxide whitewash powder craft synoptic diagram of the present invention.
Ilmenite powder is at first passed through acidolysis (8) and makes titanium liquid by known production processes of generally producing titanium liquid such as reduction, sedimentation, crystallizations, design stirring reaction (9) at this titanium liquid through hydrolysis (11) the present invention before and mix (10) two operations titanium liquid is handled, the ultimate principle of two kinds of treatment processs all is: add in titanium liquid or produce fine CaSO 4Deng sulphate particles, because CaSO 4, BaSO 4Be equal to the TiOSO in the titanium liquid 4Common SO is all arranged 2- 4Negatively charged ion, CaSO 4Certainly have at Ca Deng microparticle surfaces 2+With SO 2+ 4Between scission of link make CaSO 4Ca on the surface 2+Deng SO in the attraction titanium liquid 2+ 4, and CaSO 4Deng SO on the microparticle surfaces 2- 4Attract section H +Ion causes acidity localized variation in the titanium liquid, promotes the carrying out of hydrolytic action, forms the part automatic growing crystal species, simultaneously CaSO 4, BaSO 4Can be examined by the titanium white bag Deng also, part enters product section with polymerization state and substitutes titanium white, and does not damage its performance.
Adopt stirring reaction (9), then whole technological process is as follows: above-mentioned titanium liquid is carried out chemical reaction through stirring reaction (9), and processing condition of the present invention are as follows in stirring reaction (9):
A, with granularity less than 200 purpose CaCO 3, CaO and other can form the compound of sulfate precipitation or contain CaCO with sulfuric acid reaction 3Carbonatite, (preferably contain CaCO 3Greater than 50%) join stirring reaction in the titanium liquid, the above-claimed cpd add-on is to account for TiO in the titanium liquid 25-80%Wt for the meter.
B, low-temp reaction: T=room temperature-90 ℃, best room temperature-60 ℃, t＞0.1 hour, the best is 1-1.5 hour.
C, titanium concentration 100-400 restrain TiO 2/ liter, best 130-230 gram TiO 2/ liter, its chemical equation is:
Form part TiO 2Precipitation, this TiO 2Particulate promotes hydrolysis to carry out in hydrolytic process, promotes TiO in calcination process 2Crystallize into the titanium dioxide particle of certain type, also form portion C aSO simultaneously 4Particulate, its surperficial scission of link must attract H in the titanium liquid +, SO 2- 4, with using CaCO 3Deng and titanium liquid in acid-respons cause together in the titanium liquid that acidity reduces, quicken hydrolytic action and carry out and form the part automatic growing crystal species.While CaSO 4In product, substitute part titanium dioxide and do not influence the titanium dioxide quality Deng particulate.
Through stirring reaction (9) operation gained ti-liquid mixture again in hydrolysis (11) processing condition of the present invention be:
A, crystal seed add-on
A, production anatase thpe white powder
Room temperature-80 ℃ add down an anatase titanium dioxide crystal seed be 0-2%(by crystal seed in TiO 2With TiO in the titanium liquid 2Meter), in stirring reaction (9), add CaCO 3, above-claimed cpd such as CaO or carbonatite amount to add the crystal seed amount more at most few more.
B, production Rutile type Titanium Dioxide
Then adding the crystal seed amount is 0-5%
Other is with producing anatase thpe white powder
B, hydrolytic process
A heats up under normal pressure, makes the ti-liquid mixture boiling add the water hydrolysis, and hydrolysis time 1-5 hour, 2-35 hour was best.
B also can be in usually used pressurized hydrolysis equipment pressurized hydrolysis, hydrolysis time is 0.5-3 hour, 0.5-2 hour be the best.Also can be incubated to the boiling temperature among the a.b and carry out in room temperature.
After hydrolysis (11) is finished, handle (13) to calcining (14) through bleaching washing (12) salt again.
Processing requirement of the present invention is in calcining (14): by common method for calcinating, calcining anatase titanium dioxide temperature must not surpass 900 ℃, promptly in calcining below 900 ℃, keeps getting final product in its highest calcining temperature 10-30 minute after desulfurization.
Finish calcining (14) and just can get the titanium dioxide product after pulverize (15).Contain CaSO in this product 4Or other sulphate particles 0%-40%.
After the present invention made titanium liquid through acidolysis known operations such as (8), processing also can be handled titanium liquid by mixing (10) to titanium liquid, and in mixing (10), processing condition of the present invention are: use granularity less than 200 purpose CaSO 4Or BaSO 4Or barite, gypsum join that mixing and stirring gets final product in the titanium liquid, and then by hydrolysis (11) operation, processing condition of the present invention are in hydrolysis (11) operation:
A, titanium liquid is heated to 60 ℃-80 ℃ adds crystal seeds, crystal seed content adds CaSO according to mixing in (10) 4, BaSO 4Equal size and deciding, it is many more to add vitriol, and then the crystal seed amount of Jia Ruing is few more, and its adding crystal seed weight range anatase titanium dioxide crystal seed is 0.6%-2%; Rutilization nuclei is that 0.6%-5%(is with TiO 2The content meter).
B is warming up to the boiling hydrolysis, and hydrolysis time 1-5 hour, 2-3.5 hour was best.
C, in the existing pressurized hydrolysis jar of Producing Titanium Dioxide factory pressurized hydrolysis, hydrolysis time 0.5-3 hour.
After hydrolysis (11) is finished, successively through known bleaching washing (12) salt handle (13) calcinings (14) pulverize (15) get final product CaSO 4Or BaSO 4Part replacement of titanium dioxide titanium dioxide product, wherein CaSO 4Or BaSO 4Particulate is to become bag nuclear and polymerization state to exist with the titanium white particulate, thereby does not influence PERFORMANCE OF TITANIUM DIOXIDE PIGMENT.Above-mentioned stirring reaction (9) mixes (10) also can carry out in hydrolysis (11) hydrolytic process.
In a word, if above-mentioned technological process realizes normalizing production, quality product can reach standard laid down by the ministries or commissions of the Central Government B-101 first class product or secondary product removes TiO 2Beyond the content (because of having added CaSO 4, BaSO 4Material) every quality standard, the tinting strength of portioned product can surpass tinting strength index in the B-101 first class product.
Embodiment 1
Remove earlier operation such as ferrous sulfate and produce titanium liquid through acidolysis, reduction, sedimentation and crystallization, in the titanium liquid:
TiO 2Content: 205.9 grams per liters
Effective acid: 417 grams per liters
Ferrous: 66.67 grams per liters
F value: 2.03
Ti 3+360 grams per liters
300ml puts into hydrolytic decomposition pot with this titanium liquid: add at titanium liquid earlier and contain CaCO 390% white marble powder (granularity 200 orders) 18 gram, and fully mix reaction, after 1-2 hour in the titanium liquid mixture color shoal, be heated to 60-70 ℃ then, add anatase titanium dioxide crystal seed 0.5%, (promptly add TiO in the crystal seed 2Amount is to account for TiO in the titanium liquid 2The amount 0.5%), continue to be heated to the boiling hydrolysis, after 3 hours white metatitanic acid and CaSO 4Mixed sediment.Water carries out filtration washing to it, carries out Ti again 3+Deironing (or with zinc powder, sulfuric acid deironing): add H earlier 2SO 4To H 2SO 4Content is at 40 grams per liters and be heated to 50 ℃, adds trivalent titanium sulfate salts solution again and carries out deironing, and add-on is TiO in the trivalent titanium sulfate 2Content accounts for TiO in the titanium liquid 21% of content equals 0.6 gram, adds the back 60 ℃ of insulations 1 hour, is cooled to 40 ℃ again and washes, and when being washed to pH value=6-7, carrying out salt and handles: add earlier and account for TiO in the titanium liquid 21% K 2CO 3Be 0.6 gram, stirred 30 minutes, add P then 2O 5Account for TiO in the titanium liquid 20.1% phosphoric acid of content equals 0.06 gram, and fully stir, oven dry then, again at 800-900 ℃ temperature lower calcination, calcination process is the same with general titanium white calcination process, but top temperature should be 800-900 ℃ of scope, after the desulfurization, insulation just can obtain product to product drying after the pulverizing (dry type) in 10-30 minute under the top temperature.Titanium dioxide its each parameter such as following table:
Project The B-101 primary standard Embodiment 1 Embodiment 2
Whiteness (with standard specimenization) * Be not less than standard Suitable B-101 Suitable B-101
TiO 2Content % is not less than 97 80 85
Tinting strength % is not less than 100 97 97
Oil number % is not more than 30 30 30
Fineness (300 mesh sieve apertures, 49 tm screen excess) % is not more than 0.3 0.3 0.3
Water-soluble salt % is not more than 0.4 0.4 0.4
The water extract pH value 6.0-8.0 6.0-8.0 7
Moisture % is not more than 0.5 0.5 0.5
* the B-101 standard specimen is to build the weighing apparatus chemical plant to keep sample in 1975
Embodiment 2
Ilmenite powder is removed FeSO through common acidolysis, reduction, sedimentation, crystallization 4Make titanium liquid, in titanium liquid
TiO 2Content: 211.86 grams per liters
Effective acid: 410 grams per liters
Ti 3+: 3.66 grams per liters
FeSO 4: 60 grams per liters
500ml puts into hydrolytic decomposition pot with this titanium liquid, at room temperature adds terra alba 15 gram, and the post-heating that stirs heats up and makes ti-liquid mixture to 70 ℃, and adding anatase titanium dioxide crystal seed 1%(again is TiO in the crystal seed liquid 2Content accounts for TiO in the titanium liquid 2Content 1%), continue to be warming up to the boiling hydrolysis, after hydrolysis 2-3 hour, titanium liquid becomes metatitanic acid and CaSO 4Mixture, post precipitation carries out filtration washing to this mixture, carries out deironing bleaching again: add H earlier 2SO 4, make H 2SO 4Content adds trivalent sulfuric acid titanium salt 1% then at 40 grams per liters, is incubated 1 hour down at 60 ℃, reduces to and just can wash repeatedly below 40 ℃, carries out salt during to the PH=7 left and right sides and handles: add K earlier 2CO 3Content accounts for TiO in titanium liquid 21%, equal 0.6 gram, stir and add P again after 30 minutes 2O 5Account for TiO in the titanium liquid 20.1% phosphoric acid of weight also stirs, and the titanium white calcining process is passed through in oven dry more then, and dry type is pulverized must product, and its quality product sees the above table.
Embodiment 3
In above-mentioned example 1. examples 2. hydrolysis processs, the anatase titanium dioxide crystal seed is changed into crystal seeds of rutile just can make rutile type, its crystal seeds of rutile add-on is that example 1 adds 1%, and example 2 adds 2% and gets final product.

Claims (2)

1, the titanium dioxide method for making of using sulphate to partly replace titanium white comprises acidolysis (1) stirring reaction (2) or mixes (3), hydrolysis (4), bleaching washing (5), salt processing (6), calcining (7), pulverizing operations such as (8), it is characterized in that:
A, stirring reaction (2) process characteristic are:
Use CaCO 3, CaO and other can same H 2SO 4Reaction forms the compound of sulfate precipitation or contains CaCO 3, carbonatite titanium liquid hybrid reaction.
B, mix (3) process characteristic and be:
(comprise CaSO with granularity less than 200 purpose vitriol 4, BaSO 4, barite, gypsum) powder mixes with titanium liquid.
C, hydrolysis (4) processing condition are:
Need add crystal seed amount production anatase titanium dioxide when a. using the hydrolysis of stirring reaction (2) gained ti-liquid mixture is that 0-2%. production rutile type is that room temperature is to boiling for the 0-5%. temperature.
B. need adding the crystal seed amount when mixing the hydrolysis of (3) gained ti-liquid mixture, to produce anatase titanium dioxide be that to produce rutile type be 0.6%-5% to 0.6%-2%..
2, mixing (3) according to stirring reaction described in the claim 1 (2) should carry out before or in hydrolysis (4) hydrolytic process in hydrolysis (4).
CN 90109773 1990-12-05 1990-12-05 The titanium dioxide method for making of using sulphate to partly replace titanium white Pending CN1062125A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102646376A (en) * 2012-05-04 2012-08-22 重庆新华化工有限公司 Titanium dioxide special for retro-reflective materials
CN108299863A (en) * 2018-01-31 2018-07-20 攀枝花学院 A kind of clean preparation method of titanium white
CN109091905A (en) * 2018-09-13 2018-12-28 四川龙蟒钛业股份有限公司 Sulfuric acid method titanium pigment vacuum crystallization system and method
CN114656805A (en) * 2022-03-04 2022-06-24 河南佰利联新材料有限公司 Titanium white pigment for low-abrasion inner printing ink and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102646376A (en) * 2012-05-04 2012-08-22 重庆新华化工有限公司 Titanium dioxide special for retro-reflective materials
CN108299863A (en) * 2018-01-31 2018-07-20 攀枝花学院 A kind of clean preparation method of titanium white
CN108299863B (en) * 2018-01-31 2020-12-01 攀枝花学院 Clean production method of titanium white
CN109091905A (en) * 2018-09-13 2018-12-28 四川龙蟒钛业股份有限公司 Sulfuric acid method titanium pigment vacuum crystallization system and method
CN109091905B (en) * 2018-09-13 2021-02-23 龙佰四川钛业有限公司 Sulfuric acid method titanium dioxide vacuum crystallization system and method
CN114656805A (en) * 2022-03-04 2022-06-24 河南佰利联新材料有限公司 Titanium white pigment for low-abrasion inner printing ink and preparation method thereof

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