Method for preparing rutile phase titanium dioxide sub-microsphere through selective dispergation

The technical field of

[0001] the invention belongs to titanium dioxide nanometre material preparation field especially claims a selective rubber and preparing rutile phase titanium dioxide sub-micron ball method for.

Background technology

[0002] titanium pigment powder titanium dioxide because it has excellent brightness tinctorial strength excellent hiding power weather resistance heat resistance and chemical stability and it does not have toxicity it can be widely used for coating plastic paper printing ink and chemical fibre field such as. Present technology the application is wide titanium white powder is the anatase type a model is simply called anatase and rutile rutile is symmetrical r shape.

[0003] in recent years semiconductor titanium dioxide as a low cost effectively the light catalyst its preparation and function research by the people concerned widely. Anatase and rutile titanium dioxide is two kinds of the main crystalline phase. Anatase because it has good light catalytic activity can be widely used in the field of photocatalysis. Compared with the anatase rutile although light catalytic capability is not high but because it has good physical and chemical stability high light refractive index with strong masking power and colouring capability it can be widely used for optical material research institute coating material cosmetics and so on a plurality of domain.

[ transmitting 0004 system rutile phase titanium dioxide superfine particulate synthesis method of it is mainly composed of sol gel method microemulsion method of high temperature gas phase reaction method and so on wherein the colloidal sol gel micro-emulsion method the production cost is high reaction time is long the reaction firstly to be generated amorphous titanium oxide need to pass through the high temperature calcining can obtain rutile phase particle of the high temperature gas phase method can be directly to obtain rutile particle the reaction speed is fast it can realize continuous production but the high temperature short reaction is finished the requirement of material in quite a short time microcosmic mixing the reactor type material method for heating and a material inlet mode has high requirement of.

[0005] literature report of organic titanium or inorganic titanium as raw material it does not need high temperature treatment it is able to obtain rutile phase titanium dioxide the operation is complex the production is easy to reunite crystallization degree is not good and the problem that the.

[0006] existing technology the invention claims a lead into the iron dichloride preparing rutile type titanium pigment powder method for *** large mosh zhang yun zhang xin zang a sealing holding * liu quan shi zhan wang hong china invention # 91108973 *** x the method mainly comprises the following steps: Ilmenite sulphuric acid to obtain the titanyl sulphate solution after removing iron is led into purifying iron dichloride solution by weight of tio2: Fecl 2.4 h 20*1: 0.97 *** 3.88 freezing removing ferrous sulphate then adding i *** 6% rutile seed crystal heating water it can solve the problem of the metatitanic acid washing and rinsing and removing impurity drying grinding and then it is designed into crystal zinc oxide accelerant and mgo 750 *** 850° c the calcining 6***10 h. The method is adopted and zno crystal mgo as accelerating agent but the method of calcining in high temperature to heat preservation time is long so the actual production process of the production cost high efficiency of production is low; And the method of producing the rutile titanium pigment powder transformation efficiency is not high it is usually 95 percent as follows so the product quality affected by bigger.

[0007] the existing technology the invention also claims a microwave hot method for preparing rutile type titanium pigment powder method for *** li yuan ying william cui jun-feng cai shao-hua china invention # 97122303.3 *** the method claims a method for using the microwave radiation field the lower part of the microwave dielectric heating effect the anatase type titanium pigment powder is converted into rutile type titanium pigment powder method for. But the method for producing high device demand its preparation method complex and conversion efficiency is not high.

The content of invention

[0008] this invention is to solve the technology problem is providing a selective rubber and preparing rutile phase titanium dioxide sub-micron ball method of the obtained by the method of rutile phase titanium dioxide and small grain size 100-200nm it is evenly distributed and it does not need high temperature baking and it is easy to realize industrial production.

[0009] this invention claims a selective rubber and preparing rutile phase titanium dioxide sub-micron ball the method comprises the following steps:

[0010] mixed crystal titanium dioxide precipitate preparation of

[0011] the titanium salt with hydrochloric acid and 0.2 mol/l *** 0.5 mol/l the water solution rising temperature to 70° c at 90 degrees c i *** for keeping the temperature to obtain rutile phase titanium dioxide the precipitation obtained in the hot water it is very slow the titanium source only partially hydrolyzed; Adding lmol g/l *** 3mol per l of the inorganic alkali solution precipitating agent until the ph value is not hydrolyzed 7_9 the titanium source is converted into the anatase to obtain the anatase and rutile crystal the mixing titanium dioxide white deposition; The process of the invention is that so that water and titanium source producing rutile phase the process of the following the ph value is increased to suspend it can effectively prevent the with the hot water and the extension of the subsequent of producing the rutile in the form of rutile crystal nucleus is only growth and granularity is more rutile of the particle phenomenon.

[0012] titanium dioxide film deposited on the

[0013] the following steps then the obtained white deposition to obtain water gel the water is anatase phase and rutile phase mixed crystal titanium dioxide white precipitate and then adding 0.5 mol/l *** 1.3 mol/l inorganic acid solution to stir and disperse 70° c keeping i *** for 5h to carry out the rubber to obtain the lower layer is deposited the upper layer is light blue sol finally after the mixed liquid by centrifugation to obtain rutile phase titanium dioxide sub-micron ball.

[0014] the step of titanium in the hydrochloric acid salt of titanic chloride titanium chloride in one of or mixture of the two.

[0015] the step of the inorganic alkali into sodium hydroxide potassium hydroxide ammonia urea hexamethylene four ammonium one or several kinds of.

[0016] the step of inorganic acid is hydrochloric acid nitric acid in one of or mixture of the two.

[0017] said obtained in step of rutile phase titanium dioxide sub-micron ball the grain size is 100 200nm.

[0018] this invention claims a low temperature preparing rutile phase titanium dioxide sub-micron ball method of taking titanium hydrochloric acid as main raw material through hot water to make the titanium salt part of the water to obtain the rutile phase titanium dioxide white precipitate then adding ammonia water adjusting ph value to neutral it not the water content of titanium ion is transformed into the anatase titanium dioxide at the same time the deposition which has been changed into the anatase phase and rutile phase mixed crystal. Then using inorganic acid as the adhesive the precipitate in the anatase is changed to be stable the use of anatase phase sol deposition is changed into the grain diameter is small and evenly dispersed rutile phase titanium dioxide sub-micron ball.

[0019] this invention claims a titanium dioxide precipitate in the preparation of reaction type:

0020 ti4 + + ] [ h20 = ti02 + + + is 2h

0021 ] and [ ti02 and ti 02+4 h20 = h +

0022 ] and [ in the hydrolyzing reaction as endothermic reaction of temperature rises it is beneficial to improve the hydrolyzing rate. At the same time the hydrolysis reaction to produce large quantity of hydrogen ion will inhibit the hydrolyzing reaction of the continuously carrying out. Because of the hot water and speed of the reaction is reduced gradually high ion concentration of the rubber grain an electric double layer of the compression effect of the subsequent of producing the rutile to previously formed in the rutile crystal nucleus is used as the nucleus growth caused by the result is that with the hot water and reaction time is prolonged rutile the granule becomes larger gradually.

[0023] is neutralized by alkali to generated by the reaction of hydrogen ion which can make the hydrolysis reaction adding speed and raise the ph value is not easy to form a rutile form it is anatase phase titanium dioxide. The solution is neutralized to neutrality or weak alkali to make the solution of titanium is precipitated from the forming of rutile the process of the middle the.

[0024] in this invention uses the glue mixing method of anatase crystal in the conversion can be recycled the anatase titanium dioxide sol. After laying quietly the upper layer is anatase phase titanium dioxide sol the bottom part is rutile phase titanium dioxide microsphere ferrous deposit. The sol to transmission electron microscope observation the invention claims a method for optimizing the condition of the titanium dioxide particle size is about 100-200nm x-ray powder diffraction xrd analysis proves that titanium dioxide is rutile phase crystal grain size is about 7nm.

[0025] the beneficial effect of:

[0026] this invention has simple preparation method of mild reaction condition has no special equipment requirement;

[0027] this invention avoids the hot water in the process of rutile phase titanium dioxide submicron sphere of the continuously grows more than 400 nm adding inorganic alkali consumption is not hydrolyzed titanium source and converts it into of anatase and then through the glue removing anatase to obtain the grain diameter is the fine rutile titanium dioxide sub-micron ball 100-200nm.

Specification attached drawing

[0028] picture 1 is 1 the embodiment of the product obtained through the rutile phase titanium dioxide scanning electron microscope photo amplifying 6000 times;

[0029] 2 is an embodiment of 1 to obtain rutile crystal phase titanium dioxide x-ray diffraction pattern;

[0030] picture 3 is an embodiment of the products obtained in the rutile phase titanium dioxide sub-micron ball transmission electron microscope photo;

[0031] picture 4 is the embodiment of the 2 to obtain the anatase phase and rutile phase titanium dioxide mixed crystal of the x-ray diffraction pattern and the adhesive to obtain rutile x-ray diffraction pattern;

[0032] 5 is an embodiment of the products obtained in the rutile phase titanium dioxide sub-micron ball scanning electron microscope photo amplifier 20 000 times.

Specific implementing manner

[0033] the lower part of the combination of specific embodiment further claims the invention said. To the embodiments only can be used the invention the invention and will not be used to limit the scope of this invention. The understanding to the reading of the invention teaching the content after the field of technical personnel to the invention is various change or modifying cost and so on these form the same is located at the accessory this utility model claim a defined range of.

[0034] embodiment 1

[0035] to 0.2 mol/l for titanium tetrachloride solution of 500 ml of heating up to 70 centigrade for 8 hours keeping the temperature to obtain white precipitate under the condition of the titanium source in more than has been transformed into rutile stopping heating room temperature aging for 5h washing and drying the same shape as chart 1 of the scanning electron microscope photo of the particle diameter is about 400-500nm. And its crystal picture 2 which can be confirmed as rutile titanium dioxide crystalline phase grain size is about 7.2nm.

[0036] embodiment 2

[0037] to 0.2 mol/l for titanium tetrachloride in the lower insulating 70° c h 1.0 to watch with a shallow to form milky white surface precipitation of starting to form. Keeping 70° lmol g/l c adding the ammonia water until ph is equal to about 7.8 70° c heat preservation for 2 hours forms large quantity white deposition. The sedimentation and it cleanly washes things and 20 grams of humidity precipitate into ioomll 0mhno3 solution the deposit smashing to 700 r/min the strong stirring and the 70° h c keeping the temperature to be 2.0 stewing for 1.0 hours can observe the liquid layer the phenomenon of the upper layer is blue light coloured transparent sol and the lower layer is white deposition. By the high speed centrifugal the bottom part of sedimentation and separation it can clean.

[0038] picture 3 is the embodiment of the glue and preparation method of rutile phase titanium dioxide submicron sphere of the transmission electron microscope image can be clearly seen in the process of preparing rutile phase titanium dioxide grain diameter is small it is evenly distributed and with flower shape structure. The rubber at the front of the wet precipitate after drying of xrd and the result shows that it is anatase and rutile crystal the mixing rubber and then collecting the deposit is rutile phase titanium dioxide using xrd the result is shown as picture 4.

[0039] embodiment 3

0040 [ 0.6 ] to m50ml chloride titanium and 2.0 m50ml hydrochloric acid the mixed solution c keeping the temperature to 80 degree 1.0 h see the shallow has milk white deposition to form expressing starting to form. Keeping 80 degrees c adding 0.5 m of sodium hydroxide solution until the ph of about 80 degrees c equal to 8 the heat preservation for 2 hours forms large quantity white deposition. The sedimentation and it cleanly washes things and 35 grams of humidity precipitate into ioomll 1mhno3 solution the deposit smashing to 700 r/min the strong stirring and the lower insulating 3.0 70° c h ratio of 1.0 hours can observe the liquid layer the phenomenon of the upper layer is blue light coloured transparent sol and the lower layer is white deposition. By the high speed centrifugal the bottom part of sedimentation and separation it can clean.

[0041] 5 is picture the embodiment of the glue then deposit rutile phase titanium dioxide submicron sphere of the scanning electron microscope photo can be clearly seen so as to obtain rutile submicron ball grain diameter is small about 100-200nm obviously less than as the ratio of the hot water the product picture 1. Rubber and then collecting the deposit is metal ` red stone phase titanium dioxide using xrd the result is shown as picture 2 which is at the same the pure rutile phase.