JPH07267641A - Anatase type titanium dioxide and method for producing the same - Google Patents
Anatase type titanium dioxide and method for producing the sameInfo
- Publication number
- JPH07267641A JPH07267641A JP6078042A JP7804294A JPH07267641A JP H07267641 A JPH07267641 A JP H07267641A JP 6078042 A JP6078042 A JP 6078042A JP 7804294 A JP7804294 A JP 7804294A JP H07267641 A JPH07267641 A JP H07267641A
- Authority
- JP
- Japan
- Prior art keywords
- group
- type titanium
- titanium oxide
- metal component
- anatase
- 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.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 238000009283 thermal hydrolysis Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 8
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 239000000084 colloidal system Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- -1 amide compounds Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アナターゼ型酸化チタ
ンおよびその製造方法に関し、さらに詳しくは、結晶子
径が小さく耐熱性に優れ、触媒担体などに好適な各種の
金属成分を含有するアナターゼ型酸化チタンおよびその
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to anatase-type titanium oxide and a method for producing the same, and more specifically to anatase-type titanium oxide having a small crystallite size and excellent heat resistance, and containing various metal components suitable for catalyst carriers. The present invention relates to titanium oxide and a method for producing the same.
【０００２】[0002]
【従来技術およびその問題点】従来、酸化チタンは、顔
料や触媒担体などに広く利用されており、それぞれの用
途に適した製造方法が提案されている。例えば、特開昭
６１−１７４２２号公報には、顔料用のアナターゼ型ま
たはルチル型二酸化チタン一次粒子を硫酸チタニル希薄
水溶液中に懸濁し、該二酸化チタン一次粒子の存在下、
硫酸チタニルの加水分解を行って、見掛け粒径が１μ〜
２０μの分散性に優れ紫外線遮蔽率の高い二酸化チタン
凝集粒子の製造法が開示されている。また、特公平１−
１４８０７号公報には、硫酸チタンに微粒子ケイ酸を添
加し、熱加水分解して生成したメタチタン酸を乾燥・焼
成して得られる酸化チタンを使用して、窒素酸化物除去
用触媒を製造する方法が記載されており、特開平４−１
９７４４２号公報には、可溶性チタン化合物と、可溶性
ケイ素化合物および／またはシリカゾルとを出発原料と
して用い、水性媒体中で該原料をアンモニアによって中
和せしめて共沈物を得、該共沈物スラリーをｐＨ８．５
以上の範囲で２０時間以上熟成せしめた後、これを洗浄
し、乾燥、焼成して得られるチタンおよびケイ素からな
る二元系複合酸化物を窒素酸化物除去用触媒の成分とし
て使用する方法が開示されている。しかし、従来の方法
で得られるアナターゼ型酸化チタンは、結晶子径が大き
く、耐熱性に劣り触媒担体などの適合性の面で必ずしも
満足のいくものではなかった。2. Description of the Related Art Titanium oxide has hitherto been widely used for pigments, catalyst carriers and the like, and a production method suitable for each use has been proposed. For example, in JP-A-61-17422, primary particles of anatase-type or rutile-type titanium dioxide for pigments are suspended in a dilute aqueous solution of titanyl sulfate, and in the presence of the titanium dioxide primary particles,
Hydrolysis of titanyl sulfate gives an apparent particle size of 1μ
A method for producing titanium dioxide agglomerated particles having excellent dispersibility of 20 μm and having a high ultraviolet shielding rate is disclosed. In addition,
Japanese Patent No. 14807 discloses a method for producing a catalyst for removing nitrogen oxides, using titanium oxide obtained by adding fine particle silicic acid to titanium sulfate and drying and calcining metatitanic acid produced by thermal hydrolysis. Is disclosed in Japanese Patent Laid-Open No. 4-1.
In JP 97442, a soluble titanium compound and a soluble silicon compound and / or silica sol are used as starting materials, the materials are neutralized with ammonia in an aqueous medium to obtain a coprecipitate, and the coprecipitate slurry is prepared. pH 8.5
Disclosed is a method of using a binary complex oxide composed of titanium and silicon obtained by aging the mixture in the above range for 20 hours or more, washing, drying and firing the mixture as a component of a catalyst for removing nitrogen oxides. Has been done. However, the anatase-type titanium oxide obtained by the conventional method has a large crystallite size, is inferior in heat resistance, and is not always satisfactory in terms of compatibility with catalyst carriers and the like.
【０００３】[0003]
【発明の目的】本発明の目的は、結晶子径が小さく、耐
熱性に優れた各種の金属成分を含有するアナターゼ型酸
化チタンおよびその製造方法を提供することにある。ま
た、他の目的は、硫酸根の含有量が少なく平均粒子径が
非常に大きく、各種の金属成分が均一に分散してなる触
媒担体などに好適なアナターゼ型酸化チタンおよびその
製造方法を提供することにある。An object of the present invention is to provide anatase type titanium oxide containing various metal components having a small crystallite size and excellent heat resistance, and a method for producing the same. Another object is to provide anatase-type titanium oxide and a method for producing the same, which is suitable for a catalyst carrier and the like in which the content of sulfate is small and the average particle size is very large, and various metal components are uniformly dispersed. Especially.
【０００４】[0004]
【構成】本発明は、硫酸チタニルを周期律表第ＩＢ族、
第IIＡ族、第IIＢ族、第IIIＡ族、第IIIＢ族、第IVＡ
族、第ＶＡ族、第ＶＢ族、第VIＢ族、第VIIＢ族、第VII
I族から選ばれた少なくとも１種の金属成分を含有する
化合物の水溶液または水性コロイド溶液中で熱加水分解
によりアンモニアを発生する化合物の存在下に熱加水分
解することを特徴とする前記金属成分を含有するアナタ
ーゼ型酸化チタンの製造方法および該製造方法で得られ
たアナターゼ型酸化チタンに関する。すなわち、本発明
者らは、硫酸チタニルを前記金属成分を含有する化合物
の存在下に熱加水分解して前記金属成分を含有するアナ
ターゼ型酸化チタンを製造するに際して、前記熱加水分
解を熱加水分解によりアンモニアを発生する化合物の存
在下に行うと前記金属成分がアナターゼ型酸化チタン中
に十分に含有されること、および熱加水分解によりアン
モニアを発生する化合物の存在下に硫酸チタニルを熱加
水分解すると、粒子径の大きいアナターゼ型酸化チタン
が生成し、生成したアナターゼ型酸化チタンは硫酸根の
除去が容易で、通常の掛水洗浄で硫酸根をＳＯ4として
１．０ｗｔ％以下に除去することができることを見い出
し、本発明に到達した。[Structure] The present invention provides titanyl sulfate by group IB of the periodic table,
Group IIA, IIB, IIIA, IIIB, IVA
Group, Group VA, Group VB, Group VIB, Group VIIB, Group VII
A metal component which is hydrolyzed in the presence of a compound which generates ammonia by thermal hydrolysis in an aqueous solution or an aqueous colloidal solution of a compound containing at least one metal component selected from Group I. The present invention relates to a method for producing anatase-type titanium oxide and anatase-type titanium oxide obtained by the method. That is, when the present inventors thermally hydrolyze titanyl sulfate in the presence of a compound containing the metal component to produce anatase-type titanium oxide containing the metal component, the thermal hydrolysis is carried out. When the metal component is sufficiently contained in the anatase-type titanium oxide when carried out in the presence of a compound that generates ammonia, and when the hydrolyzed titanyl sulfate is hydrolyzed in the presence of a compound that generates ammonia by thermal hydrolysis. Anatase-type titanium oxide having a large particle size is produced, and the anatase-type titanium oxide produced can easily remove sulfate radicals, and the sulfate radicals can be removed to 1.0 wt% or less as SO 4 by ordinary washing with water. They have found what they can do and have reached the present invention.
【０００５】熱加水分解によりアンモニアを発生する化
合物としては、尿素、ホルムアミドなどのアミド化合
物、アセトアミジンなどのアミジン化合物、アミン化合
物などが挙げられる。特に尿素は好ましい。Examples of compounds that generate ammonia by thermal hydrolysis include amide compounds such as urea and formamide, amidine compounds such as acetamidine, and amine compounds. Urea is particularly preferable.
【０００６】本発明のアナターゼ型酸化チタンの製造法
において、前記熱加水分解によりアンモニアを発生する
化合物の量は、前記水溶液中の金属成分を十分にアナタ
ーゼ型酸化チタン中に含有せしめ、かつ得られる該アナ
ターゼ型酸化チタンの粒子径が大きく、硫酸根の除去を
容易にするために、硫酸チタニル水溶液中の硫酸に対
し、該化合物／硫酸（モル比）で０．５〜１０の範囲に
することが好ましい。本発明で使用される硫酸チタニル
は、オキシ硫酸チタンとも称される化合物であって水溶
液の形で使用される。硫酸チタニル水溶液の濃度は、Ｔ
ｉＯ2として０．５〜２０ｗｔ％の範囲が適当であり、
また硫酸チタニルのＨ2ＳＯ4／ＴｉＯ2の重量比は１．
４〜５．０の範囲にあることが望ましい。In the method for producing anatase-type titanium oxide of the present invention, the amount of the compound capable of generating ammonia by the thermal hydrolysis is obtained by sufficiently containing the metal component in the aqueous solution in the anatase-type titanium oxide. The anatase-type titanium oxide has a large particle size, and in order to facilitate the removal of sulfate radicals, the compound / sulfuric acid (molar ratio) is in the range of 0.5 to 10 with respect to the sulfuric acid in the aqueous solution of titanyl sulfate. Is preferred. The titanyl sulfate used in the present invention is a compound also called titanium oxysulfate and is used in the form of an aqueous solution. The concentration of the titanyl sulfate aqueous solution is T
A suitable range for iO 2 is 0.5 to 20 wt%,
The weight ratio of titanyl sulfate H 2 SO 4 / TiO 2 is 1.
It is preferably in the range of 4 to 5.0.
【０００７】また、本発明での金属成分としては、周期
律表第ＩＢ族、第IIＡ族、第IIＢ族、第IIIＡ族、第III
Ｂ族、第IVＡ族、第ＶＡ族、第ＶＢ族、第VIＢ族、第VI
IＢ族、第VIII族から選ばれた少なくとも１種の金属成
分が使用され、水に可溶な化合物が好適に使用される。
中でも、該金属成分として、Ｍｇ，Ａｌ，Ｌａ，Ｃｅ，
Ｓｉ，Ｐ，Ｖ，Ｍｏ，Ｗ，Ｍｎ，Ｆｅから選ばれる少な
くとも１種の金属成分が特に好ましく使用される。本発
明では、前記の金属成分は、該金属成分を含む化合物の
水溶液の状態か、または、平均粒子径が１００ｎｍ以下
の微粒子が分散した水性コロイド溶液の状態で使用する
ことが好ましい。前記金属成分を含む微粒子の平均粒子
径が１００ｎｍよりも大きい微粒子が水中に分散した懸
濁液では、得られるアナターゼ型酸化チタン粒子中に含
有される金属成分が均一に分散されず、凝集した状態で
存在することになるので好ましくない。好ましくは、前
記の金属成分は水溶液の状態で使用する。例えば、Ｔｉ
Ｏ2として１００重量部の硫酸チタニルに対し、前記の
金属成分を酸化物として０．１〜１００重量部、好まし
くは１〜２０重量部を水溶液中に含有させる。前記水溶
液中に含まれる金属成分の量が０．１重量部よりも少く
ない場合には、得られるアナターゼ型酸化チタン中に含
有される金属成分の量が少くなり、結晶子径が小さくな
らない。また、該金属成分の量が１００重量部よりも多
い場合には、得られるアナターゼ型酸化チタン中に含有
される金属成分の量が多くなるため、金属成分の影響が
大きくなりアナターゼ型酸化チタンとしての特性が失わ
れるので好ましくない。したがって、本発明の方法によ
り得られるアナターゼ型酸化チタンは、該金属成分を酸
化物として０．１〜５０ｗｔ％、好ましくは１〜２０ｗ
ｔ％の範囲で含有することが望ましい。Further, as the metal component in the present invention, there are group IB, group IIA, group IIB, group IIIA and group III of the periodic table.
Group B, Group IVA, Group VA, Group VB, Group VIB, Group VI
At least one metal component selected from Group IB and Group VIII is used, and a water-soluble compound is preferably used.
Among them, as the metal component, Mg, Al, La, Ce,
At least one metal component selected from Si, P, V, Mo, W, Mn and Fe is particularly preferably used. In the present invention, the metal component is preferably used in the form of an aqueous solution of a compound containing the metal component or in the form of an aqueous colloidal solution in which fine particles having an average particle size of 100 nm or less are dispersed. In a suspension in which fine particles having an average particle size of the metal component of more than 100 nm are dispersed in water, the metal component contained in the obtained anatase-type titanium oxide particles is not uniformly dispersed and is in an aggregated state. It is not preferable because it is present in. Preferably, the metal component is used in the form of an aqueous solution. For example, Ti
0.1 to 100 parts by weight, preferably 1 to 20 parts by weight, of the above-mentioned metal component as an oxide is contained in the aqueous solution with respect to 100 parts by weight of titanyl sulfate as O 2 . When the amount of the metal component contained in the aqueous solution is not less than 0.1 parts by weight, the amount of the metal component contained in the obtained anatase type titanium oxide is small and the crystallite diameter is not small. Further, when the amount of the metal component is more than 100 parts by weight, the amount of the metal component contained in the obtained anatase type titanium oxide is large, so that the influence of the metal component becomes large and the anatase type titanium oxide is obtained. This is not preferable because the property of is lost. Therefore, the anatase type titanium oxide obtained by the method of the present invention contains 0.1 to 50 wt% of the metal component as an oxide, preferably 1 to 20 w.
It is desirable to contain it in the range of t%.
【０００８】特に硫酸チタニル水溶液の濃度を、ＴｉＯ
2として２〜１６ｗｔ％の範囲に調製することにより、
得られる金属成分含有アナターゼ型酸化チタンの平均粒
子径を５μｍ以上、所望により６μｍ〜２０μｍとする
ことができる。このように平均粒子径が５μｍ以上の該
アナターゼ型酸化チタンは、円柱状やハニカム状などの
形状に成形して触媒担体に使用した場合に好適な細孔容
積・細孔分布などの細孔構造を付与するので高性能で、
かつ触媒寿命が長くなるなどの好結果をもたらす。前記
の硫酸チタニルを熱加水分解によりアンモニアを発生す
る化合物の存在下に行う熱加水分解は、６０℃以上の温
度、好ましくは９５℃以上、さらに好ましくは沸点で
０．５時間以上維持して行う。前記熱加水分解により生
成した金属成分含有アナターゼ型酸化チタンは、通常の
方法で、洗浄、乾燥、焼成される。Particularly, the concentration of the aqueous solution of titanyl sulfate is changed to TiO 2.
By adjusting the range of 2 to 2 to 16 wt%,
The average particle size of the obtained metal component-containing anatase type titanium oxide can be 5 μm or more, and if desired, 6 μm to 20 μm. Thus, the anatase-type titanium oxide having an average particle size of 5 μm or more has a pore structure such as a pore volume and a pore distribution suitable when used as a catalyst carrier after being formed into a columnar shape or a honeycomb shape. Because it gives high performance,
In addition, it brings good results such as a longer catalyst life. The above-mentioned thermal hydrolysis of titanyl sulfate in the presence of a compound capable of generating ammonia by thermal hydrolysis is carried out at a temperature of 60 ° C. or higher, preferably 95 ° C. or higher, more preferably at the boiling point for 0.5 hours or longer. . The anatase type titanium oxide containing a metal component produced by the thermal hydrolysis is washed, dried and fired by a usual method.
【０００９】本発明の方法で得られる金属成分含有アナ
ターゼ型酸化チタンは、金属成分が酸化チタン中に均一
に分散しており、空気中で５００℃−５時間焼成した時
の結晶子径が３０〜１５０Å程度で非常に小さく、耐熱
性に優れている。また、硫酸根の含有量を少くでき、平
均粒子径を大きくできるので、各種の触媒担体、顔料、
紫外線吸収剤、化粧品、インク、樹脂等の添加剤などの
分野に利用される。特に、脱硝触媒の原料として使用し
た場合には、得られる触媒は、細孔容積が大きく、耐熱
性に優れ、活性が高く、寿命が長いなどの好結果をもた
らす。以下に実施例を示し、本発明をさらに具体的に説
明する。The metal component-containing anatase type titanium oxide obtained by the method of the present invention has the metal component uniformly dispersed in the titanium oxide, and has a crystallite size of 30 when calcined in air at 500 ° C. for 5 hours. It is very small at about 150Å and has excellent heat resistance. Further, since the content of sulfate radicals can be reduced and the average particle size can be increased, various catalyst carriers, pigments,
It is used in the fields of ultraviolet absorbers, cosmetics, inks, and additives such as resins. In particular, when it is used as a raw material for a denitration catalyst, the resulting catalyst has favorable results such as a large pore volume, excellent heat resistance, high activity, and long life. Hereinafter, the present invention will be described more specifically with reference to examples.
【００１０】実施例１〜１４ ＴｉＯ2としての濃度が１２．０ｗｔ％の硫酸チタニル
水溶液（Ｈ2ＳＯ4／ＴｉＯ2重量比４．０）８．３３ｋ
ｇを還流器の付いた加熱のできるタンクに入れた。この
溶液に硫酸マグネシウム溶液（ＭｇＯ濃度１０ｗｔ％）
３０９ｇをＴｉＯ2／ＭｇＯ重量比が９７／３となるよ
うに添加した。さらに、この溶液に尿素を０．３ｋｇ添
加し、撹拌しながら、沸点（１０５℃）まで加熱し、沸
点で８時間撹拌しながら保持して熱加水分解した。得ら
れた沈殿生成物をろ過、１０リットルの水で掛水、洗浄
した後、１００℃で１２時間乾燥した。この乾燥品はＸ
線回折の結果、アナターゼ型酸化チタンの回折図を示
し、他の結晶形は認められなかった。また、該乾燥品を
空気中で５００℃−５時間焼成した酸化チタンの性状を
表１〜３に示す。酸化チタンの焼成品をＸＭＡ分析によ
り観察した結果、酸化マグネシウムは酸化チタン中に均
一に分散していた。前述の硫酸マグネシウムの代りに表
１〜３に示す各種の金属成分を含有する水溶液を用い
て、金属成分含有アナターゼ型酸化チタンを製造した。
それぞれの性状を表１〜３に示す。Examples 1 to 14 Titanyl sulfate aqueous solution having a concentration of 12.0 wt% as TiO 2 (H 2 SO 4 / TiO 2 weight ratio of 4.0) 8.33 k
g was placed in a heatable tank equipped with a reflux condenser. Magnesium sulfate solution (MgO concentration 10 wt%) was added to this solution.
309 g was added so that the TiO 2 / MgO weight ratio was 97/3. Furthermore, 0.3 kg of urea was added to this solution, heated to the boiling point (105 ° C.) with stirring, and kept at the boiling point for 8 hours with stirring to undergo thermal hydrolysis. The obtained precipitated product was filtered, washed with 10 liters of water, washed, and then dried at 100 ° C. for 12 hours. This dried product is X
As a result of line diffraction, the diffraction pattern of anatase type titanium oxide was shown, and no other crystal form was observed. Tables 1 to 3 show the properties of titanium oxide obtained by firing the dried product in air at 500 ° C for 5 hours. As a result of observing the fired product of titanium oxide by XMA analysis, magnesium oxide was uniformly dispersed in titanium oxide. An anatase type titanium oxide containing a metal component was produced by using an aqueous solution containing various metal components shown in Tables 1 to 3 instead of the above magnesium sulfate.
The respective properties are shown in Tables 1 to 3.
【００１１】比較例１ 市販の硫酸チタン水溶液にＴｉＯ2／ＳｉＯ2重量比で９
７／３となるようにシリカゾルを添加し、尿素を添加す
ることなく沸点まで加熱して熱加水分解を行った。得ら
れた沈殿生成物を実施例と同様に処理した。結果を表１
〜３に示す。Comparative Example 1 A commercially available titanium sulfate aqueous solution was mixed with TiO 2 / SiO 2 in a weight ratio of 9
Silica sol was added so that the ratio became 7/3, and the mixture was heated to the boiling point without adding urea for thermal hydrolysis. The resulting precipitated product was treated as in the example. The results are shown in Table 1.
~ 3.
【００１２】比較例２ 実施例１で使用した硫酸チタニル水溶液にＴｉＯ2／Ｓ
ｉＯ2重量比で９７／３となるようにシリカゾルを添加
し、撹拌しながら３０℃に保持した。この溶液に１５ｗ
ｔ％アンモニア水を徐々にｐＨ９．０まで滴下してゲル
を生成せしめた。この状態で２０時間熟成した後、得ら
れた沈殿生成物を実施例と同様に処理した。結果を表１
〜３に示す。Comparative Example 2 TiO 2 / S was added to the titanyl sulfate aqueous solution used in Example 1.
Silica sol was added so that the weight ratio of iO 2 was 97/3, and the temperature was maintained at 30 ° C. with stirring. 15w for this solution
A gel was generated by gradually adding t% aqueous ammonia to pH 9.0. After aging for 20 hours in this state, the obtained precipitation product was treated in the same manner as in Example. The results are shown in Table 1.
~ 3.
【００１３】比較例３ 実施例１で、尿素を添加しないほかは全く同様に処理し
た。結果を表１〜３に示す。Comparative Example 3 The same treatment as in Example 1 was carried out except that urea was not added. The results are shown in Tables 1 to 3.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【表２】 [Table 2]
【００１６】[0016]
【表３】 注）＊1 遠心式自動粒度分布測定装置にて測定。 ＊2 平均粒子径５０ｎｍのシリカゾル。[Table 3] Note) * 1 Measured with a centrifugal automatic particle size distribution analyzer. * 2 Silica sol with an average particle size of 50 nm.
【００１７】[0017]
【効果】本発明の方法で得られる各種金属成分を含有す
るアナターゼ型酸化チタンは、結晶子径が小さく、平均
粒子径が大きく、また、金属成分は均一に分散した粉末
が得られる。このようなアナターゼ型酸化チタンは、各
種の触媒担体、添加剤などに有用である。[Effect] The anatase type titanium oxide containing various metal components obtained by the method of the present invention has a small crystallite size, a large average particle size, and a powder in which the metal components are uniformly dispersed can be obtained. Such anatase type titanium oxide is useful as various catalyst carriers, additives and the like.
Claims (5)
Ａ族、第IIＢ族、第IIIＡ族、第IIIＢ族、第IVＡ族、第
ＶＡ族、第ＶＢ族、第VIＢ族、第VIIＢ族、第VIII族か
ら選ばれた少なくとも１種の金属成分を含有する化合物
の水溶液または水性コロイド溶液中で熱加水分解により
アンモニアを発生する化合物の存在下に熱加水分解する
ことを特徴とする前記金属成分を含有するアナターゼ型
酸化チタンの製造方法。1. Titanyl sulfate is added to Group IB and II of the periodic table.
Contains at least one metal component selected from Group A, Group IIB, Group IIIA, Group IIIB, Group IVA, Group VA, Group VB, Group VIB, Group VIIB, and Group VIII A method for producing anatase-type titanium oxide containing the above metal component, which comprises thermally hydrolyzing the compound in an aqueous solution or an aqueous colloidal solution of the compound in the presence of a compound that generates ammonia by thermal hydrolysis.
の製造方法において、熱加水分解によりアンモニアを発
生する化合物が尿素であるアナターゼ型酸化チタンの製
造方法。2. The method for producing anatase-type titanium oxide according to claim 1, wherein the compound that generates ammonia by thermal hydrolysis is urea.
化チタンの製造方法において、硫酸チタニル水溶液の濃
度が、二酸化チタンとして０．５〜２０ｗｔ％、硫酸チ
タニルのＨ2ＳＯ4／ＴｉＯ2の重量比が１．４〜５．０
の範囲であるアナターゼ型酸化チタンの製造方法。3. The method for producing anatase titanium oxide according to claim 1 or 2, wherein the concentration of the titanyl sulfate aqueous solution is 0.5 to 20 wt% as titanium dioxide, and the weight of titanyl sulfate H 2 SO 4 / TiO 2 is 2 . Ratio is 1.4 to 5.0
The method for producing anatase-type titanium oxide, which is in the range of 1.
型酸化チタンの製造方法において、二酸化チタンとして
１００重量部の硫酸チタニルに対し、金属成分を酸化物
として０．１〜１００重量部を使用し、前記金属成分を
酸化物として０．１〜５０ｗｔ％を含有するアナターゼ
型酸化チタンの製造方法。4. The method for producing anatase-type titanium oxide according to claim 1, 2 or 3, wherein 0.1 to 100 parts by weight of a metal component as an oxide is used with respect to 100 parts by weight of titanyl sulfate as titanium dioxide. And a method for producing anatase type titanium oxide containing 0.1 to 50 wt% of the metal component as an oxide.
Ａ族、第IIＢ族、第IIIＡ族、第IIIＢ族、第IVＡ族、第
ＶＡ族、第ＶＢ族、第VIＢ族、第VIIＢ族、第VIII族か
ら選ばれた少なくとも１種の金属成分を含有し、かつ平
均粒子径５μｍ以上のアナターゼ型酸化チタン。5. Titanyl sulfate is added to Group IB and II of the periodic table.
Contains at least one metal component selected from Group A, Group IIB, Group IIIA, Group IIIB, Group IVA, Group VA, Group VB, Group VIB, Group VIIB, and Group VIII And anatase type titanium oxide having an average particle size of 5 μm or more.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07804294A JP3366105B2 (en) | 1994-03-24 | 1994-03-24 | Method for producing anatase-type titanium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07804294A JP3366105B2 (en) | 1994-03-24 | 1994-03-24 | Method for producing anatase-type titanium oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07267641A true JPH07267641A (en) | 1995-10-17 |
| JP3366105B2 JP3366105B2 (en) | 2003-01-14 |
Family
ID=13650790
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07804294A Expired - Lifetime JP3366105B2 (en) | 1994-03-24 | 1994-03-24 | Method for producing anatase-type titanium oxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005187294A (en) * | 2003-12-26 | 2005-07-14 | Dowa Mining Co Ltd | Titanium dioxide for visible light response type catalyst and its manufacturing method |
| JP2009214045A (en) * | 2008-03-11 | 2009-09-24 | Jgc Catalysts & Chemicals Ltd | Exhaust gas treatment device |
| WO2020170918A1 (en) | 2019-02-19 | 2020-08-27 | 昭和電工株式会社 | Titanium oxide production method |
| WO2021117568A1 (en) | 2019-12-12 | 2021-06-17 | 昭和電工株式会社 | Highly heat-resistant anatarse-type titanium oxide and method for producing same |
-
1994
- 1994-03-24 JP JP07804294A patent/JP3366105B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005187294A (en) * | 2003-12-26 | 2005-07-14 | Dowa Mining Co Ltd | Titanium dioxide for visible light response type catalyst and its manufacturing method |
| JP2009214045A (en) * | 2008-03-11 | 2009-09-24 | Jgc Catalysts & Chemicals Ltd | Exhaust gas treatment device |
| WO2020170918A1 (en) | 2019-02-19 | 2020-08-27 | 昭和電工株式会社 | Titanium oxide production method |
| KR20210096194A (en) | 2019-02-19 | 2021-08-04 | 쇼와 덴코 가부시키가이샤 | Manufacturing method of titanium oxide |
| WO2021117568A1 (en) | 2019-12-12 | 2021-06-17 | 昭和電工株式会社 | Highly heat-resistant anatarse-type titanium oxide and method for producing same |
| KR20210145844A (en) | 2019-12-12 | 2021-12-02 | 쇼와 덴코 가부시키가이샤 | High heat-resistance anatase-type titanium oxide and manufacturing method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3366105B2 (en) | 2003-01-14 |
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